The Serie A club welcome Arsenal to Stadio San Paolo needing to win by three goals or better Borussia Dortmund's result at Olympique de Marseille, who are yet to pick up a point in this season's competition, in order to qualify.
Benitez will be without the injured Marek Hamsik for the clash, but hopes a raucous home crowd can inspire his players to a memorable victory.
"We can win, we believe," the Spaniard said at a press conference.
"We are working to the maximum, the fans should rest assured because the true value of Napoli will come out.
"I am sure everyone will appreciate this team over time. Tomorrow we have a great game against a very strong opponent.
"Arsenal are leading the Premier League and I think they have the best coach in the Premier League.
"We have to try to impose our game and win to our potential. San Paolo will give us a big boost. To the fans, I say we will give everything to achieve a great result.
"I wish everyone to give 100 per cent for a wonderful evening and a great challenge."
A point will be good enough to seal top spot for Arsene Wenger's side, though the Gunners could still go out of the competition if Dortmund triumph and they are overturned by three goals in Italy.