Wenger's side welcome the Serie A outfit to the Emirates Stadium on Tuesday for the second game of their Group F campaign.
Both teams started with 2-1 victories, with Arsenal winning away in Marseille and Napoli tasting home success against last season's runners-up Borussia Dortmund.
Benitez was appointed at the Stadio San Paolo in the close-season and has yet to see his side lose in Serie A.
And Wenger is anticipating a tough encounter against a familiar foe, after going head-to-head with the Spaniard during his stints at Liverpool and Chelsea.
"I think he is a top-class manager," the Frenchman said. "He has proven that. So when you are confronted with his teams you know it will always be difficult.
"But we are up for it and we have the confidence to do it.
"Our home form will be important, we have taken three points away from home. We know away from home we are in good form as well so I believe our home matches against all three teams will be important."
Arsenal sit top of the Premier League after taking 15 points from six matches and are on a nine-match winning run in all competitions, after bouncing back strongly from an opening-day defeat to Aston Villa.
They continued their fine form with a 2-1 triumph over Swansea City on Saturday, with goals from Serge Gnabry and Aaron Ramsey.
But Wenger described talk of his team being favourites for the Premier League title as "ridiculous".
"I think that our job most importantly is to find a balance between ambition and humility," he added.
"Ambition of course because we want to win but humility as well because we have only played six games. So to talk about the title today is absolutely ridiculous.
"What we
have done is just what we want to do, to continue the same ambition. I
think the team has a good humility level and is keen to improve."
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