Three-time winner Van Gerwen lost in a last-leg decider to Ryan Joyce, exiting the tournament before the knockout phase for the first time since 2010.
The Dutchman started poorly but he clawed his way back into the match by taking consecutive legs with 11 and 14 darts respectively to make it 4-4, but Joyce checked out with double 10 to complete the upset.
Joyce told Sky Sports: “I’m happy to win. It didn’t feel like a battle, it felt like we were struggling a little bit. It’s a funny old game.”
Luke Littler had almost raised the roof earlier in the night when he fell just short of a perfect leg, failing to pin double 12.
But the 17-year-old beat Lourence Ilagan 5-3 to secure a third consecutive win and set up a last-16 showdown with Mike De Decker.