Anastasia Pavlyuchenkova reached her first French Open quarter-final for a decade, while Paula Badosa and Tamara Zidansek will make their debuts as the women's last eight began to take shape.
Russia's Pavlyuchenkova beat 15th seed Victoria Azarenka 5-7 6-3 6-2.
Spain's Badosa booked her place with a 6-4 3-6 6-2 win over 2019 Czech finalist Marketa Vondrousova.
She will play Zidansek in the quarter-finals after the Slovenian beat Romania's Sorana Cirstea 7-6 (7-4) 6-1.
It means that the women's last four at Roland Garros is guaranteed to feature a player appearing in their maiden Grand Slam semi-final.
The women's draw has been left wide open after the departure of seven of the top 10 players by the end of the first week, with this half of the draw particularly badly hit.
Serena Williams, the seventh seed, is the highest ranked player remaining in this half of the draw and she faces Kazakhstan's Elena Rybakina later on Sunday (approximately 16:45 BST, follow live BBC radio and text commentary).
Pavlyuchenkova awaits the winner of that encounter.
The Russian 31st seed came into the tournament in good form, reaching the Madrid semi-finals last month, and had beaten in-form third seed Aryna Sabalenka in the previous round before her victory over two-time Grand Slam champion Azarenka.
"It's really incredible I'm still playing tennis 10 years later," said 29-year-old Pavlyuchenkova, whose last Roland Garros quarter-final in 2011 ended in defeat by defending champion Francesca Schiavone.
"It's a surprise for me to be here. I fought for each ball and each point and played very well."
Meanwhile, unseeded Zidansek had previously never been past the first round in Paris.
The world number 85 saved a set point in a tight first set before dominating Cirstea, ranked 54th in the world.
"I came out on court prepared and it was a battle," the 23-year-old said on court.
Her next opponent Badosa, 23, is a former junior champion at Roland Garros and is in great form on clay this season with 17 wins and two loses on the surface, including a title in Belgrade last month.