Horschel outduels McIlroy to win PGA Championship play-off
America's Horschel, McIlroy and South Africa's Thriston Lawrence all finished the final round on 20-under par at the course near London.
Lawrence exited the play-off with a bogey at the first extra hole, which Horschel and McIlroy both birdied.
The players returned to the par-five 18th for the second extra hole and both found the green in two, McIlroy narrowly missing his eagle attempt before Horschel holed from marginally closer.
"I'm thrilled, excited for the way I played," said Horschel, the world number 24. "Just battled out there today.
"At the same time a little disappointed -- Rory is a really good friend of mine and I think the world of him. I think he's a generational talent.
"I know how close he's been this year so I can feel for him but at the same time I'm pretty excited for just being able to get it done today."
Northern Ireland's McIlroy, ranked third in the world, has been pipped at the post on a number of occasions this year, including at last week's Irish Open, where he finished one shot behind winner Rasmus Hojgaard.
He also lost his way in the final round of the US Open as he chased a first major triumph for 10 years.
"It just shows the standard out here," said the four-time major winner.
"If you slip up just a little bit or don't make a birdie on a crucial hole, someone is always waiting to take advantage of that."
Horschel and McIlroy started the day in a tie for second, three shots behind leader Matteo Manassero.
Lawrence had set the clubhouse target following a superb closing 65, although the South African would ultimately be left to rue failing to birdie either of the two closing par fives.
That left the door open for the chasing pack and McIlroy looked set to take full advantage when he holed from distance for an eagle on the 17th and saw his approach to the 18th narrowly avoid the water to the left of the green.
However, after a poor chip McIlroy's birdie attempt from 15 feet never threatened the hole and Horschel holed out for a birdie to make it a three-way play-off.