Kerber, who only had a personal best record of a last 16 in this clay season, failed to withstand the strong forehand and backhand attacks from her opponent as she lost the first set 6-2 in 38 minutes.
German world number one Kerber, the reigning US Open champion, dropped serve six times on her way to a 6-2, 6-2 defeat to Russia's Ekaterina Makarova. She's the first women in the modern era to lose in the first round as the top seed at the French Open.
After briefly threatening a recovery in the eighth game, in which she held two break points, Kerber meekly surrendered the first set with a forehand that never looked like clearing the net.
She arrived in Paris with a 25-12 win-loss record in Grand Slam matches, but as it turns out this marks her second consecutive first-round French Open departure after losing to Kiki Bertens in the first round past year.
Another significant event of the day was a return to Petra Kvitova - champion of Wimbledon at the end of December past year, suffered an armed attack and received serious injuries, his working left hand. "It's miracle. Not even me or Petra thought she could be ready to come back so soon", said her coach, Jiri Novak.
Kvitova is set to face the victor of the match between America's Bethanie Mattek-Sand and Russian Evgeniya Rodina.
The 31st-seeded Vinci, who became a household name when she ended Williams' hopes of a calendar year Grand Slam by beating her in the semifinals at the U.S. Open in 2015, lost to Rio Olympics gold medalist Monica Puig of Puerto Rico 6-3, 3-6, 6-2.
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"As I said last time, I had already won".
"I think it doesn't really matter how I played, but I won", the 15th-seeded Kvitova said. Well, with no warm up matches heading into this tournament, Kvitova dominated her service game and had 31 winners.
The loss opens up the French Open to others such as Simona Halep.
Williams, who is seeded 10th, saved two set points to win 6-4, 7-6 (3). As the first woman to go out in the first round of French Open history is the top pick.
The 27-year-old has yet to commit to any events ahead of Wimbledon but admitted she was keen to return to a regular routine as quickly as possible.
Asked how her hand felt, she replied: "I didn't feel any differences, which is nice". Kvitova has missed all season so far while recovering from surgery on her left, racket-holding hand in December.
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