Schwartzel dropped four shots in his last five holes to enter a playoff with Englishman Sullivan, having seemingly been cruising to what would have been his maiden home championship win.
Having carded a final round 67 for a tournament total of 277, Sullivan then produced a superb iron into the green from the rough to set up the birdie chance on the first extra hole and defeat a deflated Schwartzel.
The South African had led by five shots going into the final round, but could only manage a 74 on Sunday as his game fell apart on the final five holes.
"It’s unbelievable. After yesterday, I didn’t think I stood much of a chance with Charl getting that far ahead, but I just dug in there and got myself into a position to win," Sullivan said at the trophy presentation.
He carded two birdies and an eagle on his back nine in Sunday's round and managed to take that momentum into the playoff.
He looked to be in trouble after a wayward drive, but left himself a 10 foot putt for the win after a fine iron through a cluster of trees.
"I was delighted just to hit the green and have a chance to win it. I didn't want to give him a second chance to take the title away from me," Sullivan said.
He added he hopes the beers will be flowing at his home Nuneaton Golf Club tonight.
"I try and enjoy myself as much as possible, it's something I have wanted to do my whole life and just playing on the European Tour is a dream. To win an event caps it all off."
Despite his jitters, Schwartzel still led by three shots going into the final three holes.
Then a double-bogey on the 16th and another dropped shot on the next hole left him scrambling for a par on the 18th to force the playoff, where Sullivan's greater confidence ultimately showed.
(Reporting by Nick Said in Cape Town; editing by Justin Palmer and Ian Chadband)
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