It was the visitors who took the lead early on when Andre Ayew headed home the opening goal but Napoli hit back with strikes from Gokhan Inler and Gonzalo Higuain to head into the break ahead.
Florian Thauvin looked like he had rescued a point for Marseille when he tapped in an equaliser in the 64th minute but Higuain found the winner late on to earn his side a dramatic 3-2 win.
Read below to find out how the drama unfolded in Naples.
6.45pmGood evening everyone. Napoli came out on top when these two sides met in France two weeks ago and they can move a step closer to the next round with a victory tonight. Can Marseille finally find their first point of this season's campaign?
6.47pmNapoli could move to the top of Group F if they win and the game between Borussia Dortmund and Arsenal ends as a draw. It's a big night for the top three teams.
6.50pmMarseille haven't been at their best in the Champions League, that much is obvious. However, they could have a big say in who qualifies from this group in the final three matches.
6.52pmElie Baup has claimed that his team are now playing for pride in the Champions League and suggested that his side should at least record one point in yesterday's press conference.
6.56pmPride could well be the only thing at stake for the visitors tonight but that doesn't mean that they will not cause problems for Napoli. There's certainly enough quality in the Marseille team to make this a very interesting encounter.
6.59pmWe've got full team news on the way from both sides in Naples.
7.02pmMARSEILLE: Mandanda, Abdallah, Nkoulou, Diawara, Morel, Romao, Cheyrou, Thauvin, Valbuena, A. Ayew, J. Ayew
7.05pmMarek Hamsik and Valon Behrami, who both impressed for Napoli in France a couple of weeks ago, have been left on the bench by Rafael Benitez. Goran Pandev starts for the hosts to provide support for central strike Gonzalo Higuain.
7.07pmBenitez does have a lot of options on the bench, with Lorenzo Insigne and Duvan Zapata also named as substitutes for Napoli tonight.
7.12pmJordan Ayew starts in attack for the visitors, with brother Andre expected to start just behind him. Florian Thauvin and Mathieu Valbuena are likely to provide the threat on the wings.
7.13pmBaup appears to have named a very attack-minded lineup for this game as he know his side have nothing to lose at this stage in the group stage. It looks like they'll go all out for the victory this evening.
7.15pmNapoli are expected to secure all three points today and in such a tight group, the really cannot afford to miss out against the bottom team at home. Arsenal still need to come to Naples, so a victory is a necessity tonight.
7.18pmMarseille will be well aware of the goal threat that their opponents carry this evening. Higuain is the name that sticks out on the team sheet but Jose Callejon seems to love this competition. The former Real Madrid midfielder has scored eight goals in 12 Champions League appearances.
7.21pmA 1-1 draw with Rennes on the weekend ended a run of five successive defeats for Marseille. It just hasn't clicked for Baup's men this season and they are already 10 points behind leaders PSG in Ligue 1.
7.25pmIt's a very tight group but tonight's results could change everything. Napoli know they need a victory tonight before they face their two closest rivals in the next two games.
7.28pmPREDICTION: There's just over 15 minutes left before the action begins, so it's time to guess what the score will be tonight. I think Napoli have too much quality for Marseille and the home advantage will help them record a 3-1 victory.
7.31pmI mentioned earlier that Hamsik is on the bench tonight. He was linked with a big money move away from the club only last summer and his absence shows you how far Napoli have come this season. Benitez has a very good squad at his disposal.
7.33pmIt's a cold night in Naples, with many players choosing the option to warm up in gloves. Kick off is just over 10 minutes away.
7.35pmValbuena will, as always, be a key player for the visitors tonight. The attacking midfielder only showed flashes of his quality in the game two weeks ago but his ability on the counter attack will be vital if Marseille are to cause the hosts problems.
7.38pmMarseille will surely be aggressive tonight. They can still snatch a spot in the Europa League with a bit of luck and with the pressure off, there is no reason why they should sit back.
7.40pmBoth teams are lined up in the tunnel now. Will Napoli's superb season continue? Can Marseille produce a shock tonight? Group F could look very different in a couple of hours.
7.43pmIt's not quite full inside the Stadio San Paolo but the fans will certainly create a good atmosphere for this one. Just a few handshakes away from kick off.
7.45pmHere we go then. Marseille will get the game underway.
2 minNapoli have settled pretty well but Marseille are pressing the ball in midfield, which has made it difficult so far.
4 minNapoli are applying good pressure now just outside the box and they almost create an opportunity but the assistant referee raises his flag to stop Callejon.
5 minCHANCE! Callejon plays a superb pass to Mertens, who drags his shot just wide from inside the box. That's a great opportunity wasted by the Belgian.
8 minMarseille are already showing good intent going forward and their impressive passing tempo is testing Napoli.
10 minWhat a start for the visitors! Thauvin delivers a perfect corner into the six yard box, where Ayew rises highest to head home the opening goal.
11 minThe Stadio San Paolo is in shock now. Napoli are dominating possession from the restart but they face a fight to secure the victory from this position.
13 minMarseille are looking dangerous when they attack in numbers. Valbuena earns himself some room on the left before chipping a ball to Jordan Ayew, who is unable to turn and shoot under pressure.
14 minInler plays an early ball over the top for Callejon but Mandanda reacts well to rush out of his goal to collect the pass.
16 minMarseille have been very impressive so far. They look relaxed at the back but their aggression in midfield is what is causing Napoli the most problems.
17 minThe visitors win a corner again and it's Valbuena who delivers the cross on this occasion. Reina charges off his line to take the catch though.
19 minNapoli just haven't found their passing rhythm yet in front of their own supporters. Higuain is looking too isolated in attack and there's been too many long balls hit forward.
20 minValbuena is running the game when he cuts in from the left to link up with Cheyrou, who has looked composed in possession early on. Thauvin receives the ball on the right but his cross is too deep to provide an opportunity for Jordan Ayew.
22 minWhat a strike from Inler! Marseille fail to fully clear the danger following a corner and Inler takes a touch on the edge of the box before firing in an unstoppable half volley. You won't see many better goals than that this week.
23 minThat strike should bring Napoli to life now. They've been sluggish so far but there's a lot to come.
24 minNapoli have completed a turnaround in just a couple of minutes as Higuain puts them ahead. A cross from the right is headed down by Pandev and the former Real Madrid forward drills his volley through Mandanda's legs.
26 minMarseille's confidence will have been knocked after being the better side for the first quarter of this match. Napoli are improving as the first half progresses. As it stands, they are now top of the group.
27 minThe crowd have come alive inside the ground. It's been a thrilling game so far and neither team are showing signs of sitting back at this stage.
29 minHiguain shakes his head as the offside flag is raised just before he prepares to unleash a strike at goal. Sorry Gonzalo, you had strayed too early on that occasion.
30 minThauvin uses all of his skill to find some room on the right wing but Armero sticks to his task impressively to win a goal kick for the home side.
32 minMarseille are still carrying a threat but the service to the Ayew brothers isn't what it was early in the first half. Valbuena needs to come in from the left to get involved with play more often.
33 minYELLOW CARD! Fernandez is the first player to be booked after he brings down Andre Ayew with a late challenge as Marseille looked to launch a counter attack.
35 minMarseille are still winning the battle in midfield. Cheyrou, in particular, is having a very good game.
36 minSAVE! Reina is forced into action to deny Jordan Ayew, who had earned himself some room on the edge of the box following a good run from deep.
38 minN'Koulou receives the applause from his teammates when he makes a brilliant interception to prevent Higuain from turning in a Mertens cross.
40 minJordan Ayew seems to do well to hold off a challenge from Fernandez but the referee awards the Napoli defender a free kick on the edge of his own box.
41 minThe tempo has slowed down as the half time break approaches. Napoli are looking more relaxed now but they still haven't found fifth gear.
43 minThey might be behind, but this isn't the same Marseille we've seen in recent weeks. The visitors enjoy a sustained spell of possession and Valbuena just misses out when he looks to meet a deep cross at the back post.
44 minValbuena uses his skill to create some space in the box before clipping a cross to Andre Ayew, who fails to get a shot away under pressure from a couple of Napoli defenders.
45 minThe fourth official confirms that there will be one minute of added time played.
8.33pmMarseille end the first half strongly but they can't create any opportunities before the referee blows the half time whistle.
8.35pmThe visitors started the game well and took the lead when Andre Ayew broke the deadlock with his header. However, Napoli fought back with two goals in as many minutes from Inler and Higuain.
8.36pmMarseille haven't created many chances since falling behind, with Reina only being asked to make a simple save from Jordan Ayew. Napoli are not at their best but they'll surely improve after the break.
8.39pmSome of Napoli's big players haven't made an impact yet. Callejon has only shown his quality in flashes, while Mertens and Pandev have not seen much of the ball.
8.41pmMarseille have 45 minutes to stop themselves from heading out of the Champions League. Can they dig a bit deeper to salvage something from the game?
8.43pmThe game between Dortmund and Arsenal is currently goalless. If that stays the same, and Napoli win this evening, Benitez will see his side climb to the top of the group.
8.46pmBoth sides are now heading out of the changing rooms. Napoli cannot afford to start the second half slowly against Marseille, who have shown a lot of fight tonight.
46 minNapoli launch the ball forward from the restart to Pandev, who believes he has been fouled when he loses possession on the edge of the box. The ball eventually reaches Higuain but his cross is aimed straight at Mandanda.
48 minNot much to report in the early stages of the second half. Napoli have seen more of the ball but Marseille are holding firm at the back.
49 minA Napoli attack breaks down and they're left short at the back. Thauvin cuts in from the right and a lack of options encourages him to fire a shot just wide from 25 yards out.
51 minThe referee is certainly eager to allow the game to flow but it looks like he misses a foul when Dzemaili is tripped by Cheyrou in midfield. Napoli's supporters quickly voice their anger.
52 minCLOSE! Thauvin beats a couple of defenders on the wing before unleashing a left foot effort which crashes into the side netting. I don't think Reina had that one covered!
54 minBoth teams are beginning to get a bit sloppy in possession. Neither side have been able to take control of the game early in the second half.
56 minMaggio is released on the right and he delivers an inviting cross into the box for Higuain, who is unable to control the ball under pressure.
57 minSUBSTITUTION: Valbuena is the first player to go off as Dimitri Payet is introduced.
59 minGood football from the hosts to pick out Pandev on the left but his dangerous delivery is well collected by Mandanda.
62 minMarseille haven't seen much of the ball in the last few minutes but they still look a threat on the counter attack.
64 minWhere has that come from? Napoli fail to clear a deep cross into the box and Tahuvin arrives at the back post to tap home an equaliser for his team. That could be a big goal in this group.
65 minUPDATE: The bad news keeps on coming for Napoli. Aaron Ramsey scored a few moments ago in Germany, so Arsenal would now be clear at the top of the group if the scores stay the same.
66 minSUBSTITUTION: No surprise to see this change from Benitez as Hamsik comes on to replace Pandev, who has barely had an impact tonight.
67 minSUBSTITUTION: Baup makes a change of his own as Gignac comes on for Jordan Ayew.
69 minMarseille win a free kick in a good position but Payet's delivery is too close for Reina, who collects with ease inside the box.
70 minThe visitors threaten again on the break when Gignac sprints towards the goal. Fernandez does well to catch the forward and the pressure is relieved when the referee awards a free kick to the hosts.
72 minJust 18 minutes plus stoppage time left for Napoli to find a winner from somehow. Baup said his Marseille team were playing for pride tonight and they've certainly done that much.
74 minHamsik is offered space on the edge of the box but his effort is well blocked by Morel, who then does well to clear the danger.
75 minHiguain scores a vital goal for his team! Mertens does well to create some space and he delivers a good ball across the six yard box to the Argentine striker, who converts from close range. Is that the winning goal?
77 minThat's harsh on Marseille. Napoli haven't threatened much in the second half but they are now in pole position to collect all three points.
79 minCLOSE! Callejon looks to put the result beyond doubt when he's gifted some space but he fails to hit the target with his strike from the edge of the box.
81 minYELLOW CARDS! Romao is booked for a late challenge on Dzemaili just moments after Payet is cautioned for a sloppy tackle in midfield.
82 minCLOSE! Romao's challenge gives Callejon the opportunity to unleash a shot from 25 yards but his effort just drifts past the post.
83 minSUBSTITUTIONS: Mario Lemina comes off the bench to replace Romao. Lorenzo Insigne is on for Napoli as a replacement for Mertens.
84 minWOODWORK! Great counter attacking football from the hosts as Inler sprints down the left before finding Insigne, who loses his marker and rattles the post with a brilliant strike.
85 minAlbiol fouls Gignac in a very dangerous position and the striker steps up to fire the free kick against the wall. Napoli then clear the danger as they look to hold on in the closing stages.
87 minCLOSE! The superb Thauvin shows great awareness to find Payet in space and the substitute almost finds an equaliser with a curled effort which just misses the target.
88 minCLOSE! Armero should have extended Napoli's lead. He breaks free after outpacing Thauvin but instead of waiting for help, he chooses to fire an effort wide.
90 minSUBSTITUTION: Behrami is on for the home side to replace Dzemaili in midfield. Three minutes of added time to be played.
90+1 minMarseille have tired in the latter stages of this match. Can they create one more opportunity?
9.39pmWhat a match. Marseille were unable to claim the draw that their play deserved this evening. They pay the price for four successive defeats as Baup's men are officially unable to qualify for the knockout stages.
9.40pmArsenal have managed to secure a 1-0 victory in Germany to take them to the top of the group on goal difference. Napoli also have nine points and they move into second. Dortmund drop to third, three points behind the teams above them.
9.42pmIt's not over yet, but Napoli have secured a crucial victory tonight thanks to that late winner from Higuain. Benitez will know that his side now have a great chance of reaching the next round.
9.44pmThanks for joining me tonight. I hope you've enjoyed the coverage and make sure you stick with Sports Mole as we bring you reaction from across the continent. Goodnight.