The Serie A club welcome Arsenal to Stadio San Paolo needing to win, while also hoping injury-ravaged Borussia Dortmund slip up at Marseille, who are yet to pick up a point in this season's competition.
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.
A point will be good enough to seal top spot for Arsene Wenger's side, who could still go out of the competition, if Dortmund triumph and they are overturned by three goals in Italy.
"We can win, we believe," the Spaniard said.
"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 is leading the Premier League and I think they have the best coach of the Premier League.
"Wenger will prepare the race focusing on the quality of his men, as well as we do.
"They prefer possession but they also know to share. 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 gives 100 per cent for a wonderful evening and a great challenge."
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