Napoli are the only unbeaten side in Italy and want to build the Champions League momentum too by hosting Benfica.
It kicks off at the Stadio San Paolo at 19.45 UK time (18.45 GMT).
The Partenopei had a dream start in Europe and summer signing Arek Milik bagged a brace in their 2-1 victory away to Dynamo Kiev.
They are also the only Serie A team without a defeat so far this season and are hoping to build more confidence going forward.
This represents a return to the Peninsula for ex-Inter goalkeeper Julio Cesar, while defender Viktor Lindelof has been heavily linked with a move to Napoli, Juventus or Inter.
The San Paolo crowd hasn’t had the chance to sing ‘The Champions’ along to the tournament theme tune for two years, so expect an earth-shaking rendition before kick-off.