The pair exchanged the lead on numerous occasions during the final round at Augusta but after missing one putt to win in regulation play, Garcia birdied the first playoff hole after Rose could only make a bogey.
The triumph for the Spaniard came on what would have been the 60th birthday of his compatriot and idol Seve Ballesteros, while he was able to remove the tag of being the player with the third-most Major appearances without ever claiming the title.
Garcia began Sunday on level terms with friend and playing partner Rose, but he wasted little time in opening up a two-shot lead as the chasing pack failed to put together a run of birdies.
However, he started to encounter trouble on the back nine - at the same time that Rose began to find his rhythm on the greens - and when Garcia sent his tee shot into the trees on the 13th, Rose had his chance to open up what could have been an unassailable advantage.
Remarkably, Garcia would make par, like Rose who only managed a three-putt, and he came alive on the 14th and 15th as he recorded a birdie and eagle respectively to ensure that the duo went to the 16th hole sharing the lead and with a four-shot lead over the field.
Rose held top spot on his own thanks to a birdie and Garcia missing a short putt, but he gave the shot away when bogeying the 17th and it set up what will go down as one of the most memorable 15 minutes in the tournament's prestigious history.
Both men played the perfect hole up until the green where Rose missed a seven-foot birdie putt to hand Garcia his chance, but he rolled a shorter - but arguably more testing putt - wide of the hole and they would soon replay the last.
Rose's wayward drive opened up the door for Garcia and he took the opportunity with both hands, replicating his tee shot and approach from 20 minutes earlier before rolling in a 15-foot putt to seal his crowning moment.