Barca and English champions Chelsea finished in the top four in the league phase and qualified directly for the quarter-finals, alongside Bayern Munich and record eight-time winners Lyon.
To set up the mouthwatering encounters, Real Madrid must first beat Paris FC in the knockout play-offs, while Arsenal face a rematch with Belgians OH Leuven, who they beat 3-0 in the final league phase matchday on Wednesday.
In the other knockout ties, Manchester United will face Atletico Madrid, with the victors set to meet Bayern Munich, and Wolfsburg take on Juventus for the right to play Lyon in the last eight.
The two-legged knockouts will take place between February 11th to 19th, with the quarter-finals scheduled for March 24th to April 2nd.
Draw
Knockout play-offs:
Real Madrid (ESP) vs Paris FC (FRA)
Manchester United (ENG) vs Atletico Madrid (ESP)
Juventus (ITA) vs Wolfsburg (GER)
Arsenal (ENG) vs OH Leuven (BEL)
Quarter-finals:
Real Madrid or Paris FC vs Barcelona (ESP)
Manchester United or Atletico vs Bayern Munich (GER)
Juventus or Wolfsburg vs Lyon (FRA)
Arsenal or OH Leuven vs Chelsea (ENG)
Semi-finals:
Real Madrid or Paris FC or Barcelona vs Manchester Utd or Atletico or Bayern
Juventus or Wolfsburg or Lyon vs Arsenal or OH Leuven or Chelsea