LaLiga giants Barca enjoyed 17 consecutive seasons playing in the Champions League knockout stages before their run was ended this season.
The Catalan powerhouse dropped out of Europe's elite competition after finishing third in their group behind Bayern Munich and Benfica.
Napoli meanwhile finished second in a Europa League group behind Spartak Moscow that saw Leicester end up third.
Barcelona v Napoli: Date and start time
This Europa League clash will take place on Thursday, February 17.
The Nou Camp fixture is scheduled for a 5.45pm kick-off in the UK.
These two sides last met in the Champions League in 2020 when Barcelona secured a 3-1 win on route to a 4-2 aggregate triumph.
Barcelona v Napoli: TV channel and live stream
This Diego Maradona derby will be broadcast live on BT Sport ESPN with live coverage starting from 5:30pm.
BT Sport customers can live stream this via the app using their mobile, tablet or computer devices.
To tune in to talkSPORT or talkSPORT 2, click HERE for the live stream.
App iPhone - Download from the Apple store
Android - Download from Google Play
Radio - talkSPORT is available across the United Kingdom via DAB digital radio and on 1089 or 1053 AM
TV - Listen to talkSPORT through your TV on the following channels: Sky: Channel 0108 Virgin Media: Channel 927 Freeview: Channel 723 Freesat: Channel 731
Barcelona v Napoli: Team news
Pierre-Emerick Aubameyang could make his full debut for the hosts potentially alongside Adama Traore and Ousmane Dembele.
Barca remain without Samuel Umtiti, Ansu Fati, Sergi Roberto, Ronald Araujo and Alejandro Balde through injury.
Clement Lenglet and Memphis Depay are also fitness doubts while Dani Alves has not been included in their Europa League squad.
Napoli meanwhile have both Matteo Politano and Hirving Lozano injured but otherwise have a clean bill of health to contend with.
On-loan Manchester United defender Axel Tuanzebe will not be involved after he wasn't registered in the Europa League squad.
Barcelona v Napoli: What has been said?
Barcelona boss Xavi hinted that want-away winger Ousmane Dembele could make his starting XI.
"We don't rule out that he can play at home or away," he told his pre-match press conference.
"Whether he plays or not depends only on how the players train and who is better or worse. He can play.
"He already did it against Espanyol and he helped us a lot for 20 minutes."