The Spanish side were held 1-1 in the first leg at Camp Nou as Ferran Torres missed several chances to put his side in charge of the draw.
As things stand, Napoli will be keen to make the most of the home advantage and book their place in the last 16.
Barcelona are unbeaten in their last five matches, however, and approach the match in Italy with plenty of confidence after a resounding victory against Valencia at the weekend.
New signing Pierre-Emerick Aubameyang scored a hat-trick in that victory and was part of the Arsenal squad that beat Napoli in the Europa League quarter-finals in 2019.
Where to watch Napoli vs Barcelona
TV channel: The match will be broadcast on BT SportESPN
Direct: BT Sport subscribers will be able to watch the game via the BT Sport app.
LIVE coverage: You can follow all the action via Standard Sport’s LIVE match blog.