Li Na helped Stan Wawrinka set an unwanted record after joining her fellow Australian Open champion in losing in the first round of the French Open.
Li's 7-5 3-6 6-1 loss to Kristina Mladenovic came around 16 hours after Wawrinka was dumped out by Guillermo Garcia-Lopez and it is the first time ever that the ignominious double has occurred.
Second seed Li won the title in Paris three years ago but only made the second round last year.
Mladenovic has been having a poor year in singles, dropping outside the top 100, and it looked like Li had turned things around when she won the second set.
But the Chinese player was having one of her wild days and Mladenovic dominated the deciding set before bursting into tears at her moment of victory.
Li is the first Australian Open women's champion to lose in the opening round in Paris since Lindsay Davenport 14 years ago.
Fourth seed Simona Halep had no such problems, the Romanian narrowly missing out on a double bagel on her way to a 6-0 6-2 victory over Russia's Alisa Kleybanova.
Halep's rise up the rankings over the past year has been remarkable and this was only her second ever win in the main draw at Roland Garros.
It was also her debut on Court Philippe Chatrier, and things could not have been going better when she led 6-0 5-0 only to be broken when she served for the set.
She said: "I was thinking at that moment at 5-0 that I can win 6-0 6-0, but that wasn't too good. I was a little bit relaxed after that, and it was cold. I felt a little bit in my back.
"But I stayed focused after two games lost, and then I served really well."
Former French Open champion Svetlana Kuznetsova is always a threat on clay and she was an easy 6-3 6-1 winner over qualifier Sofia Shapatava.