Didier Drogba's header on 88 minutes dramatically cancelled out Thomas Muller's opener just five minutes earlier. Both teams could not be separated in extra-time after Arjen Robben's spot-kick was saved by Petr Cech. In the shoot-out, Bastian Schweinsteiger and Ivica Olic missed for the Bavarians before Drogba buried the championship kick.
Di Matteo's men may have become overnight heroes in the blue half of west London, but it has been a tumultuous campaign for the club in Europe. From a potential group-stage elimination to a sensational comeback against Napoli to the stunning triumph over Barcelona, the Blues have negotiated their fair share of obstacles, and they have climbed to the top of the mountain.
Goal.com looks back at Chelsea's remarkable roller-coaster ride in this season's Champions League en route to a historic triumph.
Good start | Ballack couldn't hold off his former club as Chelsea won 2-0 in group opener
Remember me? | Mata returned to Valencia to help Chelsea earn a 1-1 draw at Mestalla
Five-star show | Meireles & Torres scored the first three goals in 5-0 victory over Genk
Late shock | Leverkusen netted a 90th minute winner to shock the Blues 2-1
Waltzing through | A 3-0 win at Stamford Bridge in the do-or-die clash sent Chelsea into last 16
Naples nightmare | Lavezzi & Cavani crushed Chelsea 3-1 in the last 16
Revival begins | Di Matteo guided the Blues to stunning 4-1 comeback win over Napoli
Torres thunder | El Nino inspired Chelsea to victory at Benfica in the quarter-final first leg
Settle down | Meireles' late strike against Benfica sealed Chelsea's place in the final four
Drog day | Drogba stunned Barca at the Bridge with the only goal of the first leg
Lifeline | Ramires sparked Blues' comeback as he pulled a goal back against Barca
Who me? | Terry cost himself a place in the final by getting sent off
Adios | Torres rounded Valdes to end Barca's challenge at Camp Nou
Agony & Ecstasy | Lampard revelled in Chelsea's triumph as Messi was left stunned
Blues brothers | Chelsea celebrated their passage to Munich
Mullered | Chelsea stared at defeat when Bayern scored seven minutes from time
Didier drama | Drogba sent the final into extra time with an 88th-minute equaliser
Cech mate | The Blues keeper saved former team-mate Robben's penalty in extra time
Spot on | Drogba rolls home Chelsea's winning penalty in the shoot-out
Celebration time | The Blues celebrate on the pitch after beating Bayern 4-3 on penalties
Kings of Europe | Chelsea lift Champions League trophy for the first time in their history