Holders Manchester City will play Copenhagen in the last 16 of the Champions League, while Arsenal face Porto.
Copenhagen, who finished above Manchester United in their group, reached the knockout stage for the first time since 2011.
The first legs take place on 13-14 or 20-21 February and the second on 5-6 or 12-13 March.
City and Arsenal are seeded, meaning they will play the second leg at home.
Record 14-time winners Real Madrid meet RB Leipzig, while Inter Milan – runners-up last season – play Atletico Madrid, and Bayern Munich face Lazio.
Last-16 draw
Porto v Arsenal
Napoli v Barcelona
Paris St-Germain v Real Sociedad
Inter Milan v Atletico Madrid
PSV Eindhoven v Borussia Dortmund
Lazio v Bayern Munich
Copenhagen v Manchester City
RB Leipzig v Real Madrid