The Italian giants travel to the Spanish capital while Lionel Messi and Co meet familiar opponents after being paired with the Rossoneri for the third year in a row.
Nine-time European champions Real Madrid have been paired with Juventus in the pick of Thursday afternoon's Champions League draw in Monaco. Carlo Ancelotti's men and the current Serie A champions, who met in the final in 1998, have been joined by Galatasaray and Copenhagen in Group B.
Barcelona and AC Milan will resume rivalries again after meeting four times in the last three seasons, with Lionel Messi inspiring the Blaugrana to a memorable comeback at the last 16 stage last time round. Joining them in an intriguing Group H is Ajax and Celtic.
Arsenal face a difficult task in maintaining their record of consistently reaching the knockout stages after being joined in Group F by Marseille, Napoli, and last season's beaten finalists, Borussia Dortmund.
Elsewhere, holders Bayern Munich will take on Manuel Pellegrini's Manchester City for the second time in three years, and Real Sociedad are rewarded for their play-off victory over Lyon with a trip to Old Trafford to take on Manchester United.
The 2013-14 final will be held in the Estadio da Luz in Lisbon.