Bayern Munich have an added motivation factor with the Champions League final to be staged at the Allianz Arena next May.
Coach Jupp Heynckes admits he has already started to dream about winning the Champions League.
"I think it is legitimate to think about it [the final] and it spurs my team on to think about that," he said.
"But we are in a competition with Manchester United, Barcelona and Real Madrid and maybe some other strong teams too.
"Certainly the three I have mentioned are the favourites, but then again, why would it not be possible for us to reach the final too?
"First we have to get through the group stage, though, and that is my priority right now."
Napoli currently lie in 5th spot in Serie A and have lost two out of their last four games in their domestic league, including a 2-1 loss to Catania at the weekend.
However, the Italian side have impressed during their debut season in the Champions League.
They are unbeaten and sit two points behind the Bavarians and one point clear of third-placed Manchester City at the half-way stage of Group A.
A victory over the Italian side, more famous perhaps for their past association with Argentinian superstar Diego Maradona, would virtually seal Bayern's passage to the knockout stage.
"Of course we are in a good position and we want to cement that with a win," said in-form midfielder Toni Kroos.
"If we do win, we will be very well placed for the last two games and for our aim of winning the group.
"We have achieved nothing yet and we have to bear that in mind."
Bayern are almost at full strength with only injury-prone Dutch winger Arjen Robben still on the mend. Bastian Schweinsteiger and Daniel van Buyten look to have shaken off knocks sustained during the weekend's predictable rout of Nuremberg to take their place in the starting line-up.
FCB dominated the recent Group A Champions League game in Naples but had to settle for a 1-1 draw with Mario Gomez having a tame penalty saved in the second half.
The record German champions have made the Allianz Arena a fortress - scoring 33 goals without reply in the process of winning their last eight home matches in all competitions.
Napoli can welcome back on-loan striker Goran Pandev to their ranks. Bayern fans will have painful memories of Pandev's last trip to Munich in March whilst with his parent club Inter Milan. The Macedonian scored the decisive goal for then holders Inter as the Italian giants derailed the Bavarians Champions League hopes under Louis van Gaal.
Kick off at the Allianz Arena is at 20:45
Prediction: Bayern Munich 2 Napoli 0