The Germans saw off Inter Milan in the last round, while the Italians defeated Dynamo Moscow to seal their progress.
Wolfsburg were dominant in the last round as they secured their passage into the last eight with a convincing 5-2 aggregate victory over Inter Milan.
Dieter Hecking's side have been in superb form as of late, putting together a seven-game unbeaten run in all competitions that has included six wins.
While the Bundesliga title race looks to be over as Bayern Munich race towards glory, Wolfsburg remain the Bavarians' nearest challengers in the table. Three wins and a draw from their last four matches mean that they are 10 points behind Pep Guardiola's runaway leaders.
However, Wolfsburg will be looking to Kevin De Bruyne and Bas Dost to fire them into the semi-finals. The pair have found the net 22 times between them so far this season. Dost is currently the team's top scorer with 13 goals in all competitions.
Recent form: LWWDWW
Recent form (all competitions): WWDWWW
Napoli coach Rafael Benitez will want to make it a 55th birthday to remember when he takes his players to Germany.
The Spaniard's future has recently come under question, with some reports suggesting that he could take over at Manchester City should Manuel Pellegrini get the boot.
Benitez guided the Neapolitans into the last four thanks to a 3-1 aggregate win over Dynamo Moscow. A comfortable first-leg victory all but sealed their place in the next round before the sides played out a goalless draw in Russia.
This is the first time that Napoli have reached the quarter-finals of a European tournament since 1989. That year, they went all the way to the final in the UEFA Cup before beating Stuttgart over two legs.
Despite enjoying a strong run in Europe, Napoli have seen their Serie A title bid fall by the wayside in recent weeks due to a poor run of form. While they got back to winning ways on the weekend against Fiorentina, a five-game winless run before that has seen them slip 20 points behind leaders Juventus.
Recent form: DWWWWD
Recent form (all competitions): LDDLLW
Wolfsburg midfielder Aaron Hunt will miss the game due to a knee problem, but Dieter Hecking has no further injury concerns to worry about.
Andre Schurrle could start the match after settling for a place on the bench against Hamburg.
Wolfsburg possible starting lineup:
Benaglio; Vieirinha, Naldo, Knoche, Rodriguez; Guilavogui, Arnold; Perisic, De Bruyne, Schurrle; Dost
Napoli possible starting lineup:
Andujar; Maggio, Albiol, Koulibaly, Strinic; David Lopez, De Guzman; Callejon, Hamsik, Mertens; Higuain
Head To Head
This is the first time that the two sides have met in a competitive fixture.
We say: Wolfsburg 2-1 Napoli
There is little to separate the teams heading into the match, but Wolfsburg's better form and the fact that they have home advantage means that the Germans could well sneak this one. The hosts currently have the wind in their sails, while Napoli are struggling to find a consistent level of performance.