Both players finished on nine under par after 72 holes, setting up a sudden-death play-off on the 18th.
Garcia, 37, holed a birdie putt for victory after his European Ryder Cup team-mate could only manage a bogey.
Justin Rose congratulates Sergio Garcia
— Justin Rose (@JustinRose99) April 10, 2017
It's hard not to feel good for him. I felt like I had it wrapped up at one point.
The Spaniard held his nerve as he secured his maiden Major at the 74th time of asking.
And while Rose was disappointed to lose to Garcia, he congratulated his opponent on his first Major.
Justin Rose said he was pleased for Sergio Garcia on his maiden Major victory
English golfers at the 2017 Masters
Tue, April 4, 2017
Express Sport runs through the field of English golfers chasing the green jacket at the 2017 Masters
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Express Sport runs through the English golfers competing at the 2017 Masters
Rose said: ”It's hard not to feel good for him. I felt like I had it wrapped up at one point.
"When Sergio was in the trees on 13 it looked pretty good but this course allows people to make a comeback.
"I felt like I did virtually everything right."