Last season's beaten finalists took control of the match after the half-hour mark when Daniel Sturridge and James Milner scored in quick succession, although Thomas Meunier responded just as quickly to halve the deficit going into the break.
It looked as though Kylian Mbappe had rescued an undeserved point for the underwhelming French champions when he tucked home from PSG's first second-half shot in the 83rd minute, but Roberto Firmino netted a 93rd-minute winner to ensure that the points went to Liverpool.
Find out how all of the action unfolded courtesy of Sports Mole's minute-by-minute updates below.
These two both broke the previous goalscoring record in the group stages of last season's competition and boast two of the best attacks in world football, so we should be in for plenty of entertaining football tonight. It is a match fit for the final, and we're being treated to it on matchday one!
Let's get started with a look at the team news...
Well, the headline news is that Roberto Firmino misses out for Liverpool after suffering that horrendous-looking eye injury against Tottenham Hotspur at the weekend.
The Brazilian was caught by Jan Vertonghen and subsequently taken to hospital and, while the injury was not as serious as it could have been, he is only deemed fit enough for the bench this afternoon as Daniel Sturridge comes in in his place.
Firmino has scored in Liverpool's last two games as well and also netted 10 times in 13 Champions League outings last term, matching the 10-goal tallies of Mohamed Salah and Sadio Mane as the trio became the most prolific in the competition's history.
Georginio Wijnaldum scored his first away Premier League goal at the 55th attempt at the weekend, while last season James Milner registered nine assists in this competition - a single-season record which surpassed the previous tally of a certain Brazilian called Neymar.
Alexander-Arnold and Robertson will have a big role to play as they look to maintain their attacking threat down the wings while also watching out for Mbappe and Neymar behind them, while Van Dijk and Gomez have the chance to test their blossoming partnership against some of the very best in the world right now.
Neymar, Edinson Cavani and Kylian Mbappe have already scored 11 league goals in just four games between them this season, picking up exactly where they left off before Neymar's injury in February of this year.
We also cannot forget about Cavani, who has scored eight goals in 14 appearances against English teams and netted for the third league game in a row at the weekend.
Verratti is also suspended for this game and so drops out of the team in one of three changes from the weekend win over Saint-Etienne, with Diarra and Draxler also missing out.
The personnel could also comfortably slip into a 4-2-3-1 formation too, with Di Maria joining Neymar, Mbappe and Cavani in what would be a deadly front four.
Whatever happens it should be an absolute cracker between two attack-minded teams in fine form, with both Liverpool and PSG having made perfect starts to their domestic campaigns and subsequently sitting top - or joint-top in Liverpool's case - of their respective leagues.
Chelsea have also won all five of their games so far, though, meaning that Liverpool still come into this match sitting second in the table on goal difference, although it has been a fine start to a season which promised so much.
The Reds could well have dethroned the now three-time reigning champions of Europe had Loris Karius not made two career-defining errors, while Gareth Bale capped off Madrid's win with a stunning bicycle kick. Still, few even expected them to reach the final, so they can still be very proud of their achievements in this competition last season.
This looks like a more balanced Liverpool side, though, with their defensive solidity being the foundation of their perfect domestic start to the season rather than the swashbuckling attacking which won so many admirers last term.
Liverpool also became the first team to have three players scored 10 or more goals in a single European Cup or Champions League season, with Salah, Firmino and Mane all reaching double figures.
The Reds remained unbeaten here in this competition last season, winning five and drawing two games including qualifiers. Indeed, they are now unbeaten in their last 16 European home games, stretching back to a 3-0 loss at the hands of Real Madrid in October 2014.
It is worth remembering that Liverpool only qualified for the Champions League once during a seven-year spell before 2017-18, when they made it to the final while also securing their place in the tournament this season.
PSG have monopolised the silverware in France and begin every season as overwhelming favourites to lift all of the domestic trophies, but when it comes to the Champions League their best showing remains the semi-finals from way back in 1995.
PSG made it to the quarter-finals four years in a row prior to this ongoing two-year streak, but they have so far been unable to make the next step. The club's owners have made no secret of their desire to win the Champions League, and it is their performances in this competition which define their season as a success or a failure.
Tuchel's predecessor Unai Emery won the domestic treble last season but was sacked after only reaching the last 16 of the Champions League, so Tuchel - who succeeded Jurgen Klopp as Borussia Dortmund manager, incidentally - must make progress in this competition if the season is to be deemed a success.
PSG have since won all five of their Ligue 1 matches too, scoring a whopping 17 goals in that time and already moving five points clear of the chasing pack. Indeed, the champions are just one win away from equalling their best-ever start to a Ligue 1 season, which was set last year.
If last season's Champions League group stages are anything to go by, though, they have more than enough firepower to pick up a famous victory at Anfield tonight, even if it comes to simply outscoring the hosts' own deadly front three.
As I have already mentioned, Liverpool also broke the previous record but still found themselves two goals behind PSG, who have now found the back of the net in each of their last 16 Champions League outings.
Defeat tonight would therefore condemn PSG to their worst-ever European run, and it would also see them lose three Champions League away games in a row for the very first time - although they have visited Bayern Munich, Real Madrid and now Liverpool for those games.
In truth, I have no idea where to even start in predicting this match! One thing does seem certain - goals - but the result really could go either way and either side are more than capable of scoring four, five or more tonight, such is the attacking talent on show. I will sit on the fence and go for a score draw!
SPORTS MOLE SAYS: Liverpool 2-2 PSG
PSG took control of proceedings with a 3-0 home win in the first leg, but goals from Robbie Fowler and Mark Wright threatened a comeback for Liverpool at Anfield as they fell just short. That is PSG's only previous visit to this stadium.
The French outfit have also only kept one clean sheet in their previous 12 such games - holding Chelsea to a goalless draw in the 2004-05 group stages.
In all European competition Liverpool have won their last two home matches against French sides, though, and have won 11 of 14 home games against Ligue 1 opposition.
LIVERPOOL STARTING XI: Alisson; Alexander-Arnold, Van Dijk, Gomez, Robertson; Milner, Henderson, Wijnaldum; Salah, Sturridge, Mane
PSG STARTING XI: Areola; Meunier, Silva, Kimpembe, Bernat; Rabiot, Marquinhos, Di Maria; Mbappe, Cavani, Neymar
Robertson whips a beauty of a cross into the box after Alexander-Arnold's delivery went all the way through, and Sturridge has peeled off his man to thump a header past Areola!
It is a mindless challenge from Bernat to give away the spot kick as he dangles a leg out to trip Wijnaldum, who had three other PSG defenders around him. There is no doubt that it is a penalty, and Milner makes no mistake by putting it beyond the reach of Areola!
Di Maria's initial cross into the box wasn't the best and Cavani missed with an attempted bicycle kick, but it then bounced off the leg of Robertson and fell to Meunier, who did not have a second thought before volleying it past Alisson and into the bottom corner.
43 - Since the start of last season, Liverpool have scored 43 Champions League goals; 10 more than any other team in the competition in this period. Juggernaut. #LIVPSG pic.twitter.com/FZfqfTFXjZ— OptaJoe (@OptaJoe) September 18, 2018
Liverpool have been the better team so far and looked as though they might punish a lacklustre PSG performance until the visitors pulled one back.
Sturridge was selected ahead of Firmino due to the Brazilian's eye troubles, and he has repaid Jurgen Klopp's faith so far with a goal on his first ever Champions League start for the club.
Milner stepped up to take the spot kick, and calmly tucked his finish into the bottom corner despite Areola guessing the right way.
The striker did not make contact with it, though, and the ball bounced off the leg of Robertson to fall to Meunier. The full-back still had plenty to do from there, but he made no mistake with an instinctive finish.
Salah put the ball into the back of the net, but it is chalked off for a foul by Sturridge on Areola in the PSG goal. In retrospect it is probably the right decision, but it was a late call and seemed to come from the official behind the goal.
The Reds are trying to launch a counter, but for the second time in quick succession Salah gives the ball away carelessly. Neymar pounces on it and drives forward before being tackled by Van Dijk. The ball squirms to Mbappe inside the box, and he takes a touch before tucking it into the bottom corner.
Milner wins the ball off Mbappe just outside the PSG area and feeds it to Firmino, who twists and turns inside the box before drilling a fine effort across goal and into the corner.
Liverpool make a statement in their opening match of the Champions League campaign with a 3-2 victory over a PSG side who were underwhelming and outplayed for long spells by the hosts.
Quickfire goals from Daniel Sturridge and James Milner gave Liverpool the lead in the first half, only for Thomas Meunier to halve the deficit just as quickly. It looked as though Liverpool might be punished for their profligacy when Mbappe tucked away an 83rd-minute equaliser, but Firmino came off the bench to fire home the winner in stoppage time, sending Anfield wild in the process.
Thank you very much for joining Sports Mole for tonight's thrilling Champions League opener as Liverpool beat PSG 3-2 at Anfield courtesy of Firmino's last-gasp winner. I will leave you with our match report, and be sure to stick around for reaction too.
From me, though, it is goodbye for now!