Aside from Milan, knocked out in the last 16 last term, Pep Guardiola's Spanish giants will also face FC Bate Borisov of Belarus and Viktoria Plzen in Group H.
Milan and Barca clashed in the 1994 final, with the Italians then managed by Fabio Capello dishing out a 4-0 drubbing to their Spanish rivals in Athens.
Manchester United, making a record 17th appearance in the world's top club competition, were the first of the 32 teams to be drawn out of UEFA's 'hat' by Portuguese legend Luis Figo.
Sir Alex Ferguson's three-time winners face Benfica, the Portuguese double winners from the early 1960s, FC Basel and Romanian outfit FC Otelul Galati in Group C.
United and Benfica met in the 1968 final, with the English footballing superpower prevailing for the first of their titles 4-1 on home turf at Wembley.
Figo's former club, nine-time kings of Europe Real Madrid, come up against old foes Lyon of France, Dutch heavyweights Ajax (drawn in Real's group last term), and Dinamo Zagreb.
Friday's 32-team draw featured 11 previous winners and five newcomers, with among the debutantes Ferguson's 'noisy neighbours', Manchester City.
Roberto Mancini's expensively assembled side were handed a tricky assignment with four-time winners Bayern Munich, who had to come through the play-offs, keeping them company in Group A.
Also on City's radar are Italian group stage first timers Napoli and Villarreal.
Bayern Munich's director of sport Christian Nerlinger said his side would have a tough time in Group A.
"This is a demanding group, but Bayern are the favourites," said Nerlinger, with the Champions League final on May 19 next year set to be hosted at Bayern's Allianz Arena in Munich.
"I would have preferred to have faced other teams, but we are pleased to accept the challenge. The team is up for it."
Arsenal's tricky start to the season with star players Cesc Fabregas and Samir Nasri leaving the Emirates Stadium for pastures new was eased by their defeat of Udinese in the play-offs.
And the Gunners' reward for securing their 14th Champions League campaign was a match-up against Didier Deschamps' Marseille, Borussia Dortmund and Olympiakos.
Chelsea, the fourth representative from the Premier League and last season's quarter-finalists, are in Group E with Valencia, Chelsea new recruit Juan Mata's old club, Bayer Leverkusen and Genk.
Last season's quarter-finalists and three-time champions Inter Milan come up against Russian outfit CSKA Moscow, Lille and Trabzonspor, called up to replace Fenerbahce who were denied taking up their group stage ticket over a match-fixing probe, in Group B.
Group G comprises another former winner of the competition in FC Porto, who face Shakhtar Donetsk, Zenit St Petersburg and APOEL Nicosia.
The long road to the final at Bayern's Munich stadium starts on September 13 with the opening salvos of this season's group stages
The top two placed teams in each group advance to the first knockout round, with the third-placed teams dropping down to the Europa League.
Barcelona face AC Milan, United set Portuguese test
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