The Partenopei are assured of a place in the last 32 of the Europa League but they cannot take top spot from Dnipro, with PSV unable to finish any higher than third.
But the Group F clash will still have plenty of spice seeing as the Dutch club claimed a humiliating 3-0 victory over Mazzarri's men in the early season reverse.
Uruguayan striker Cavani, scorer of 16 goals in all competitions so far, has usually started from the bench in the Europa League but he will start.
Mazzarri told the Corriere dello Sport: "Cavani will be satisfied because I'll play him tomorrow [Thursday]. He offers us something different physically and it's up to him to play well.
"(Goran) Pandev is feeling better, he could be on the bench and even get a few minutes' run out.
"We've made certain choices in Europe to avoid losing points in the league and I think we've saved about 12 with this method.
"Cavani asked me if he could play and I have a good feeling that he will do well."
Napoli defender Andrea Dossena added: "Qualifying was our objective and we've done that. Now we have to go out and avenge a 3-0 loss that really upset us."
Ominously for Dick Advocaat's PSV, the Azzurri are unbeaten at home in Europe since 1994.
The Boeren travel to Naples on the back of consecutive Eredivisie defeats and Advocaat will be without the services of Ola Toivonen, Dries Mertens, Mark van Bommel and Jetro Willems.
Defender Joshua Brenet, 18, has travelled to the San Paolo.