Williams was once again chasing a record 24th Grand Slam singles title but her wait will go on heading into Wimbledon later this month.
From the moment the 21-year-old Rybakina, playing in only her seventh Grand Slam main draw, held her opening two service games without dropping a point, Williams looked in peril.
And so it proved as seventh seed Williams bowed out to add yet another twist to a wildly unpredictable women’s event.
With so many big names having fallen, including Victoria Azarenka early in the day, a prospective quarter-final opponent for Williams, the path to the final looked enticing.
But Williams, whose last Grand Slam title came in 2017 at the Australian Open, was unable to find her A game.
She remained philosophical in defeat, however, saying that her expectations coming into the tournament had not been high.
“I’m in a much better place than when I got here,” the American told reporters.
“You know, I was just literally trying to win a match, because it had been a really difficult season for me on the clay. Although I love the clay, I was, like, if I could just win a match. That’s kind of where I was kind of coming in.”
Additional reporting by Reuters.