The 24-year-old Belgian, who combined with world number three Rory McIlroy for three points over the opening two days, went two down after starting with a bogey and a par on a sun-kissed day at Hazeltine National.
Pieters, however, came storming back with a scintillating sequence of seven birdies in 14 holes as he fully vindicated captain Darren Clarke's decision to award him a wildcard pick for the biennial team event.
It was all over for Holmes when a wayward approach shot at the par-five 16th sailed 30 yards left of the green and Pieters celebrated with an extravagant fist pump when he sank his winning birdie putt.
The previous best haul by a European rookie was the three and a half points collected by England's Paul Way in 1983 and by Sergio Garcia of Spain and Scotland's Paul Lawrie in 1999.
"It's different when you're out there on your own," said a smiling Pieters. "You don't have anyone to high-five or pick you up when you're down.
"I made plenty of birdies and that's what you need in match play. I knew that Darren believed in me, that gave me a lot of confidence."
Pieters featured in all five sessions of Europe's 17-11 defeat and acknowledged it had been a draining week.
"I'm exhausted right now," he said. "They've been really long days, getting up at 4am.
"Dealing with these crowds isn't easy, it takes a lot out of you."
(Editing by Andrew Both)
