Roberto Mancini's side may not have to face any domestic champions, but theirs is the standout group - with four-time champions Bayern determined to get to the final at their own Allianz Arena, Villarreal able to boast plenty of Champions League experience in recent years and Napoli emerging as one of the most exciting sides in Europe over the past 12 months, led by Marek Hamsik and Edinson Cavani.
Elsewhere, holders Barcelona will meet Italian champions AC Milan in one of the more enticing group stage match-ups, though those two will be comfortable favourites to progress from Group H, which also includes BATE Borisov and Viktoria Plzen.
Manchester United will have the chance to avenge the hurt of their 2005-06 Champions League campaign when they take on Benfica in Group C - the Red Devils finished bottom of their group six years ago after losing to the Portuguese giants in their final group game. FC Basel and Romanian minnows Otelul Galati make up what appears to be a fairly straightforward group for United, who were beaten by Barcelona at Wembley in May.
Group E provides a renewal of old acquaintances as Juan Mata makes an immediate return to Valencia with Chelsea, while former Blues midfielder Michael Ballack will be back at Stamford Bridge with Bayer Leverkusen. Belgian champions Racing Genk will face an uphill task to qualify as the group's fourth team.
Real Madrid and Lyon meet again, in Group D, as Jose Mourinho attempts to repeat the success he enjoyed against Les Gones in last season's second round, when the Spanish side won 4-2 on aggregate. Real will also be reunited with Dutch champions Ajax, whom they beat home and away in the 2010-11 group stage. Dinamo Zagreb make up the numbers.
In Group B, Inter Milan were drawn with CSKA Moscow, whom they beat in the quarter-finals on their way to glory in the competition in 2010, as well as French champions Lille and Trabzonspor.
After beating Udinese in Wednesday's play-off to progress, Arsenal will take on Marseille, Olympiakos and Borussia Dortmund in Group F, while Porto, Shakhtar Donetsk, Zenit St Petersburg and APOEL will collide in Group G.
After the group stage draw, Lionel Messi was named the winner of inaugural UEFA Best Player in Europe Award for 2010-2011. Messi's team-mate Xavi and Real Madrid's Cristiano Ronaldo were the other nominees.
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