Liverpool face Tottenham in what will be only the second all-English Champions League final next month, 11 years after domestic rivals Manchester United beat Chelsea in a dramatic penalty shoot-out in Moscow.
United were looking to secure another European triumph to add to their Premier League crown, having held off Liverpool's title challenge and edging out Barcelona in the semi-finals.
Chelsea, meanwhile, had battled past the Reds in their semi-final to reach the Champions League final for the first time.
Cristiano Ronaldo made the breakthrough for United at the Luzhniki Stadium with his 42nd goal of the season, heading in at the back post from Wes Brown's cross after 26 minutes.
Chelsea keeper Petr Cech saved a diving header from Carlos Tevez and then denied Michael Carrick from the rebound.
It proved a key moment as the Blues then fought back to equalise just before half-time.
Michael Essien's attempted shot from 25-yards took two deflections on its way towards goal, the most telling was off the back of United captain Rio Ferdinand.
It changed the direction of the ball into the path of Frank Lampard, who duly supplied the finish from six yards.
The second half proved a somewhat scrappy affair, with the weather conditions worsening.
With 12 minutes left, Didier Drogba's 20-yard effort had Edwin Van Der Sar beaten, but cannoned back off the post.
United sent on Ryan Giggs to make his 759th appearance for the club, breaking Sir Bobby Charlton's record.
As the final went into extra time, Chelsea were denied again by the woodwork when Lampard's shot crashed against the crossbar.
At the other end, Blues captain John Terry cleared a goalbound effort from Giggs off his own line.
With tempers boiling over, an ugly melee resulted in Drogba becoming only the second player – after Arsenal keeper Jens Lehmann in 2006 – to be sent off in a Champions League final.
The Ivory Coast forward was shown a red card by Slovakian referee Lubos Michel for slapping United defender Nemanja Vidic.
Tevez, around whom the original incident centred, and Chelsea midfielder Michael Ballack were also booked.
With neither side able to break the deadlock, the European Cup was settled by the lottery of spot-kicks.
All of the first four penalties were scored, before Ronaldo saw his effort saved by Cech.
With a chance to win the trophy for the London club, Terry stepped up to take Chelsea's fifth penalty, but his standing foot slipped just as he went to kick the ball, which spun onto the outside of the post.
As the shoot-out eventually moved to sudden death with the scores locked at 5-5, Ryan Giggs slotted in – before Van Der Sar proved the hero when he saved Nicolas Anelka's shot to seal a third European Cup triumph for United.
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