Wenger learnt a lot about the Italians when they drew 2-2 in a pre-season tournament and is also very familiar with their manager Rafael Benitez from the Spaniard's time managing in the Premier League with Chelsea and Liverpool.
Napoli are unbeaten in all competitions under Benitez, who was appointed in May, and Wenger has identified the Italian side's breakaways as their big strength and earmarked diminutive playmaker Lorenzo Insigne as key to that threat.
"He is mobile, he is not tall but quick and very good in the transition from defence to attack," Wenger told Arsenal Player. "He is a good dribbler as well and is an intelligent mover. That makes him an interesting prospect.
"That's what struck me as well in the (pre-season) Emirates Cup - when they win the ball they come out very quickly with (Jose) Callejon, (Marek) Hamsik, Insigne and (Gonzalo) Higuain, (who) come out like bombs all the time they win the ball.
"The transition from our side from offence to defence will have to be very quick."
Premier League leaders Arsenal, who went two points clear with a 2-1 win at Swansea City on Saturday, have enjoyed an excellent start to the season including their European group opener when they beat Olympique Marseille 2-1 in France.
Napoli are in similarly good shape and kicked off their continental campaign with a 2-1 victory over last year's Champions League runners-up Borussia Dortmund which Wenger believed would give them extra confidence.
Even though Arsenal were beaten by Napoli to the signature of striker Gonzalo Higuain in the close season, they are proving to be an exciting attacking prospect with Aaron Ramsey scoring eight goals in nine games and new signing Mesut Ozil shining.
Wenger will be without winger Theo Walcott who has undergone surgery on an abdominal injury, while Abou Diaby, Lukas Podolski and Alex Oxlade-Chamberlain are also sidelined.
Appearing in the group stage of Europe's elite club competition for a 16th consecutive season, Arsenal know from experience that collecting six points from the opening two games would put them well on the way to the knockout stages.
"We have started very well but you know if you win the second game at home you have a good chance to qualify," Wenger said. "It's a game that will have a great weight on the end result of the qualifying teams."
Napoli, who have scored 14 goals in six Serie A matches with Hamsik, Callejon and Higuain netting 10 of them, enjoyed a 2-0 win over Genoa on Saturday despite starting with some of their key players on the bench with a view to Tuesday's game.
"I am consistent rather than courageous. I have experience and have been in Europe many times, so I know squad rotation is necessary to make everyone in the side stronger," Benitez told Sky Sport Italia.