The Spain international faces up to a month on the sidelines due to a muscular problem
The Spain international was an unused substitute as Barca thrashed Eibar 5-0 on Saturday but Roberto, who can play at right-back or in the centre of midfield, is not part of the squad for the last-16 first-leg fixture in Naples.
Barca confirmed Roberto will miss around three to four weeks of action via a statement on their official website, which means he will also miss a vital top-of-the-table clash at Real Madrid next weekend.
“The latest casualty, Sergi Roberto, has been confirmed as having injured one of the adductor muscles in his right thigh and will be out for between two and three weeks,” the club said.
The 28-year-old has been a regular for the Catalans this season, having played 29 times and has returned a couple of assists and a single goal, which was scored against Getafe on February 15.
One of the quirkier additions on Barca’s squad list for Napoli – albeit his name was accompanied by an asterisk – was Martin Braithwaite, who cannot play in the Champions League as he is not registered.
Barca’s victory over Eibar and Madrid’s defeat at Levante on Saturday means Quique Setien’s men sit top of La Liga by two points. However, Roberto’s injury is the latest to have limited Setien’s options for upcoming fixture.
The Catalans will travel for the midweek match without Luis Suarez, Ousmane Dembele and Jordi Alba – all regulars in their starting XI – while they have called up six players from the B squad for the trip to the Stadio San Paolo.
Barcelona squad to face Napoli on Tuesday, February 24
Ter Stegen, Semedo, Pique, Rakitic, Sergio Busquets, Arthur, Messi, Neto, Lenglet, Griezmann, Braithwaite, De Jong, Vidal, Umtiti, Junior, Inaki Pena, Riqui Puig, Alex Collado, Ansu Fati, Ronald Araujo and Sergio Akieme.