Lorenzo Insigne starts with Dries Mertens as Napoli face Paris Saint-Germain’s Neymar, Kylian Mbappe, Edinson Cavani and Marco Verratti.
It kicks off at 20.00 UK time (19.00 GMT) at the Parc des Princes.
The Partenopei are group leaders going into this week, still unbeaten on four points followed by Liverpool and PSG on three.
Carlo Ancelotti returns to his old hunting ground and is reunited with Verratti, who is back from injury to start in the PSG midfield.
Verratti is also a current Italy teammate of Lorenzo Insigne and his former Pescara teammate, as they were together with Ciro Immobile at Pescara under Coach Zdenek Zeman.
Gianluigi Buffon continues to sit out the ban he was given for insulting the referee when Juventus were eliminated by Real Madrid last season, so Alphonse Areola – who was in negotiations for a move to Napoli this summer – starts in goal.
Dani Alves and Thiago Silva are big losses in defence, with Layvin Kurzawa and Colin Dagba also struggling.
Insigne has shaken off a muscular problem to start with Mertens rather than Arkadiusz Milik, while Jose Callejon and Fabian Ruiz start, surprisingly benching Piotr Zielinski, in what could well be a return to the old 4-3-3 formation or even a 3-5-2.
Simone Verdi, Faouzi Ghoulam, Vlad Chiriches Amin Younes and Sebastiano Luperto are out of action, but Nikola Maksimovic is again chosen at right-back for a more defensive approach.
There are circa 3,000 Napoli fans in Paris this evening, although only 1,200 are expected to be in the away end.
These sides have met only once before in the 1992 UEFA Cup, with a draw in Paris and French victory in Naples.
Napoli have a generally good record in France, losing only on penalties to Toulouse in the 1986 UEFA Cup, along with three wins and a draw.
Most recently, they earned a 2-1 victory in Marseille in 2013 and 2-0 Champions League play-off win in Nice.
Paris Saint-Germain: Areola; Meunier, Marquinhos, Kimpembe, Bernat; Rabiot, Verratti; Mbappé, Di Maria, Neymar; Cavani
PSG bench: Cibois, Kehrer, Nkunku, Draxler, Diaby, Choupo-Moting, Nsoki
Napoli: Ospina; Maksimovic, Albiol, Koulibaly, Mario Rui; Allan, Hamsik, Fabian; Callejon, Mertens, Insigne
Napoli bench: Karnezis, Hysaj, Malcuit, Zielinski, Diawara, Rog, Milik
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