The clash at the Stadio San Paolo will be the first between the two teams and also a Champions League debut for Barcelona coach Quique Setien and Napoli's Gennaro Gattuso, who took over after the group stages.
France's Samuel Umtiti was preferred over compatriot Clement Lenglet in the Barcelona defence, while in midfield Ivan Rakitic is joined by Sergio Busquets and Frenkie De Jong.
Gattuso has opted for captain Dries Mertens up front with Lorenzo Insigne and Jose Callejon.
Teams:
Napoli (4-3-3)
David Ospina; Giovanni Di Lorenzo, Nikola Maksimovic, Kostas Manolas, Mario Rui; Fabian Ruiz, Diego Demme, Piotr Zielinski; Jose Callejon, Dries Mertens, Lorenzo Insigne (capt)
Coach: Gennaro Gattuso (ITA)
February 25, 2020
Barcelona (4-3-3)
Marc-Andre ter Stegen; Nelson Semedo, Gerard Pique, Samuel Umtiti, Junior Firpo; Sergio Busquets, Frenkie de Jong, Ivan Rakitic; Antoine Griezmann, Lionel Messi (capt), Arturo Vidal
Coach: Quique Setien (ESP)
February 25, 2020
Referee: Felix Brych (GER)