Roberto Di Matteo's side produced an impressive second leg performance at Camp Nou to qualify for next month's final thanks to goals from Ramires and Fernando Torres
Early Barcelona pressure failed to produce results thanks to some resolute defending but that changed when Sergio Busquets turned home a low cross.
A pivotal moment in the game came when John Terry was shown a straight red card following an altercation with Alexis Sanchez on the edge of the Chelsea penalty area. At that point it looked destined that Barcelona would seal their place in the final.
A frantic 10 minutes before half-time saw Barcelona double their lead through Andres Iniesta but Chelsea instantly responded with a delightful finish from Ramires to put the visitors ahead on aggregate.
The second half was equally as hectic and when Didier Drogba fouled Cesc Fabregas in the area. Lionel Messi stepped up but smashed his spot kick against the crossbar.
Barcelona continued to have the lion's share of possession but were found wanting in terms of the final product. Isaac Cuenca and Lionel Messi forced fingertip saves from Petr Cech and the hosts also had a goal ruled out for offside.
The final nail in the Barcelona coffin came from a long clearance upfield which has latched onto by much maligned Fernando Torres with every Barcelona player in the opposite half.
The Spanish international rounded Victor Valdes and slotted into the net to cap a brilliant defensive performance by the Blues and seal an unlikely place in the final. The 7/4 on a Chelsea victory in Munich is bound to be popular with punters who can foresee a dream end for Roberto Di Matteo's men. The other semi-finalists are Real Madrid who are now 5/4 favourites and Bayern Munich at 9/4.
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Jim Knight is Betting Editor at Goal.com and has been tipping football games since he was old enough to place a bet. He is a Leicester City fan, writer and member of the We Are Going Up Podcast