Ivanovic headed home three minutes into extra time to settle an enthralling encounter in which Liverpool made a full contribution but paid the price for missed opportunities.
Chelsea were favourites after a 1-1 draw at Anfield in the first leg - but Liverpool were true to the word of manager Brendan Rodgers and played without fear, seeking their first trophy since winning this competition in 2012.
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Chelsea 1-0 Liverpool Highlights ( HD ) 27/01... paylaşan: sanagoree And Chelsea boss Jose Mourinho, who missed Ivanovic's decisive goal as he was in a heated debate with fourth official Phil Dowd, showed how much another trip to Wembley meant to him by celebrating wildly with his staff at the final whistle.
It was a result that helped banish Chelsea's embarrassment of losing 4-2 at home to League One Bradford City in the FA Cup fourth round in their previous outing.
Liverpool will leave Stamford Bridge with regrets, especially after a horrendous headed miss by Jordan Henderson in front of an open goal that could have taken the game to penalties.
There may also be a price to pay for Chelsea as striker Diego Costa may face retrospective punishment for two stamps on Emre Can and Martin Skrtel that were not seen by referee Michael Oliver.
Costa, as usual, was involved in all of the action and should have been awarded a penalty when he was brought down by Skrtel in the first half, while the Spain international's head-to-head clash with Liverpool captain Steven Gerrard earned both players yellow cards.
Mourinho will set that aside for now as he remains on course for his first piece of silverware since returning to Chelsea at the start of last season.
As expected, Liverpool did not risk striker Daniel Sturridge even though he is approaching full fitness after a series of injuries that have sidelined him since August, but Rodgers adopted a bold approach that should have brought dividends in the first half.
Keeper Thibaut Courtois was Chelsea's hero at Anfield and he twice came to the rescue here as Liverpool twice opened up Chelsea for the two best opportunities of the half, first when Gerrard picked out Alberto Moreno and then when Philippe Coutinho broke through after wrong-footing Kurt Zouma.
Chelsea, however, had a major grievance of their own as they seemed to be refused a clear penalty when Costa was brought down by Skrtel as he attempted to guide the ball into touch.
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