Reigning British Open champion Molinari defeated five-time major victor Phil Mickelson 4 and 2 as Europe took an insurmountable edge over the favoured Americans in the biennial team showdown at Le Golf National.
Tommy Fleetwood and Francesco Molinari, who can become the first European players to compile a flawless 5-0 record in the Ryder Cup, will take on Tony Finau and Phil Mickelson in matches five and nine respectively.
"This means more than majors, more than anything", said Molinari, who won all four pairs matches with Tommy Fleetwood in another European first.
Francesco Molinari set an incredible new record after playing a decisive role in Europe's Ryder Cup victory over USA. Behind them, Woods was hanging tough against Jon Rahm and Dustin Johnson started to pull ahead of Ian Poulter.
Jordan Spieth was blown out 5 and 4 by lowest-ranked player on the European team, Thorbjorn Olesen of Denmark.
"I think anyone of us would have deserved to clinch the winning point", Molinari said, "and I was nearly hoping Sergio was going to do it because I knew he was going to become the guy with most points (in Ryder Cups)". The second hole of that encounter was halved in a triple-bogey six, and Noren was enduring a particularly torrid time. The former UCLA player went through Q-school as a reinstated amateur and turned professional again at the start of the season.
"I was not playing my best, " Mickelson said.
Thomas Bjorn's men gained revenge for their defeat at Hazeltine two years ago, sending the United States to a sixth straight loss on European soil dating back to 1993.
Europe brought five rookies to Le Golf National who sure didn't seem like rookies - Alex Noren and Fleetwood were the last two French Open champions on the Albatross Course - and certainly didn't play like that. "So it can go any way, but really, really, really happy with how it's gone these first two days".
In truth, even before he came undone on the last hole, McIlroy's round had felt like it was stuck together by glue and rope, ready to come apart at any time, and that he could be punished at the end for not capitalizing on earlier opportunities to put Thomas away.
"I don't usually cry, but I couldn't help it, what a week", said the Spaniard.
"More than anything, I think the feeling we have with each other, how well we connect with each other, how much fun we have in the team room, how many options we have in foursomes and fourballs - it makes it a little bit easier", Garcia told NBC.
The inability to find a suitable Ryder Cup partner for Woods is extremely puzzling.
Molinari was just as good on his own as he was with Tommy Fleetwood, and the best year of his golfing life somehow got better.
In total, the Americans had played only eight competitive rounds at the course before the event, compared with 236 for Europe.
Jim Furyk's captain's picks finished 2-10-0 with both wins coming from Tony Finau (pending DeChambeau finish). "There is a job to be done still and we are going to do it". "Obviously they had probably the strongest team ever and were just so good".
"I just tried to do things well and be professional". I'm proud to be on this team and proud to be standing next to those other 11 teammates and proud to win a point. Bjorn picked him anyway, saying he was the heart and soul of the European team, and Garcia responded by going 3-1.