Barcelona get Napoli in Champions League Round of 16 draw
While Barcelona won La Liga last season under former club captain Xavi Hernandez, they have failed to find their feet this campaign and sit in third place in the league table, seven points off the top.
Defending champions Manchester City will take on Copenhagen in the UEFA Champions League last 16, while Arsenal will face Porto.
The draw also pitted La Liga and Serie A champions against each other, with Barcelona set for another tussle with Napoli on Europe's biggest stage.
Unseeded Paris Saint-Germain escaped the big names as they were drawn against Group D winners Real Sociedad.
Arsenal will play Porto in the UEFA Champions League last 16, while title holders Manchester City take on Copenhagen.
City won the treble last season under Pep Guardiola when they defeated Inter Milan in the final, completing a clean sweep of the major trophies available to the team.
While they have not reached the heights they did last season in the Premier League, in part due to an injury to Kevin De Bruyne, they topped Group G by winning every single one of their six matches in Europe.
The draw is one that City will be heavy favourites to negotiate regardless of any injury concerns, while they are also unsure when they can recall Erling Haaland, who is a doubt for them in the upcoming Club World Cup.
FC Porto, winners in 2004 under Jose Mourinho, were drawn against Arsenal, who continue to impress under Mikel Arteta and are attempting to compete on two fronts.
Arsenal are the only other Premier League side to reach the Champions League knockout rounds after Manchester United and Newcastle United were both eliminated in the group stages.
Italian champions Napoli, who have struggled in Serie A since the departure of Luciano Spalletti in the summer, were drawn against FC Barcelona.
While Barcelona won La Liga last season under former club captain Xavi Hernandez, they have failed to find their feet this campaign and sit in third place in the league table, seven points off the top.
Barcelona are set to contest the four-team Spanish Super Cup in Saudi Arabia in January before European tournaments restart.
Paris Saint-Germain are yet to win the Champions League and behind the scenes rumours of disquiet continue, but with Kylian Mbappe in decent form they are heavy favourites against Basque side Real Sociedad.
Last season's beaten finalists, Inter Milan, continue to impress domestically in another competitive Italian season, and they come up against another side with their own league ambitions, Diego Simeone's Atletico Madrid.
PSV Eindhoven will play German side Borussia Dortmund while Bundesliga champions Bayern Munich take on Lazio.
The first legs will take place across 13-14 and 20-21 February next year, with the return matches across 5-6 and 12-13 March.
CHAMPIONS LEAGUE LAST 16 DRAW
- Porto v Arsenal
- Napoli v Barcelona
- PSG v Real Sociedad
- Internazionale v Atletico Madrid
- PSV Eindhoven v Borussia Dortmund
- Lazio v Bayern Munich
- Copenhagen v Manchester City
- RB Leipzig v Real Madrid