They will hope to find a way through for a deep run in this year's competition with Lionel Messi enjoying another sensational season.
However, Napoli won't be dispatched easily despite their underwhelming term in Serie A so far.
The Italians are sixth in their domestic top flight, way off the pace of the top three, but have enjoyed a strong form in recent weeks with four wins out of five – including a victory over Juventus.
RadioTimes.com has rounded up everything you need to know about how to watch the Napoli v Barcelona game on TV and online.
What time is Napoli v Barcelona?
Napoli v Barcelona will kick off at 8:00pm on Tuesday 25th February 2020.
What channel is Napoli v Barcelona?
The game will be shown live on BT Sport 3 from 7:15pm.
There are multiple ways to get BT Sport. If you already have BT Broadband, you can add BT TV and Sport to your existing contract from just £15.00 per month. You can add the ‘Big Sport’ package for £40 per month which includes all BT Sport and 11 Sky Sports channels via a NOW TV pass.
How to live stream Napoli v Barcelona
You can watch the match with a BT Sport monthly pass without signing up to a contract.
Regular subscribers can also stream matches via the BT Sport website or BT Sport app on a variety of devices including laptops, smartphones and tablets.
It's hard to justify describing Barcelona as 'struggling' right now considering they're top of La Liga and going strong in the Champions League.
However, they are not at their imperious best.
Messi certainly is, but the Catalan giants have edged through most games this season as opposed to dominating teams on a weekly basis.
Napoli are the clear underdogs but will force Barca to work hard for a reward.
Prediction: Napoli 1-2 Barcelona
