Problem-hit Li stunned at French Open
China's Li Na returns the ball to France's Kristina Mladenovic during their French tennis Open first round match at the Roland Garros stadium in Paris on May 27, 2014 - by Miguel Medina
Li, the 2011 champion, went down 7-5, 3-6, 6-1 to the 103rd-ranked blonde Frenchwoman -- the Roland Garros junior champion in 2009 -- to suffer her first opening round defeat in Paris in eight visits.
The 2hr 06min loss on a windswept and chilly Suzanne Lenglen court saw Li undone by 37 unforced errors.
Mladenovic, who was Australian Open mixed doubles champion this year with Daniel Nestor, goes on to face Alison Riske of the United States.
"It didn't matter who I was playing today I still would have lost. The problem was myself. I threw myself away," said Li.
It is a familiar scenario for Li who failed to get beyind the fourth round of the six Grand Slams which followed her 2011 Roland Garros breakthrough.
"I had no idea in my mind how to play the match. The first match at a major is always tough, the tension is different. You never know what will happen."
Mladenovic, who was 36 in the world last August, was in tears after her victory, her third over a top 10 player.
"It's just incredible," she said. "I don't have the words to describe what just happened. To beat the world number two in the first round at Roland Garros, it's incredible."
Li's shock defeat means that both Australian Open champions have been knocked out in the first round after Stan Wawrinka's listless defeat on Monday.
Also making an early exit on Tuesday was Bulgarian men's 11th seed Grigor Dimitrov who lost 6-4, 7-5, 7-6 (7/4) to giant Croat Ivo Karlovic.
Karlovic fired 22 aces and wasn't broken by Dimitrov who won the Bucharest claycourt title this spring and was a semi-finalist at the Rome Masters having seen off the Croat on the way.
"It's never easy to play against Ivo. It's a big disappointment for me, losing first round of the tournament. I liked my chances here," said Dimitrov.
The 35-year-old Karlovic, whose last win in Paris was seven years ago, has now equalled his best French Open performance and next faces either Daniel Brands of Germany or Austria's Andreas Haider-Maurer.
Romanian fourth seed Simona Halep reached the second round with a 6-0, 6-2 win over Russia's Alisa Kleybanova and next plays Heather Watson of Britain.
- Date-Krumm, 43, beaten -
Other early winners were Svetlana Kuznetsova, the Russian 27th seed and 2009 champion, who beat Georgia's Sofia Shapatava 6-3, 6-1 while 43-year-old Kimiko Date Krumm of Japan, a semi-finalist in 1995, lost 6-3, 0-6, 6-2 to Russian Anastasia Pavlyuchenkova, the 24th seed.
Spanish fifth seed David Ferrer, last year's runner-up to Rafael Nadal, began his 12th Roland Garros by coasting past Igor Sijsling of the Netherlands, 6-4, 6-3, 6-1.
Ferrer, 32, has reached the quarter-finals or better at his last nine majors.
Britain's Andy Murray, the seventh seed, starts against Andrey Golubev of Kazakhstan.
Murray, 27, the Wimbledon champion, was a semi-finalist in 2011 but skipped the 2013 tournament through injury.
Former women's champion Ana Ivanovic, the Serb 11th seed, plays French world number 43 Caroline Garcia.
Ex-world number one Caroline Wozniacki, the 13th seeded Dane, tackles Belgium's Yanina Wickmayer in her first outing since her romance with golfer Rory McIlroy ended.
A quarter-finalist in 2010, the 23-year-old won her first six meetings against Wickmayer before the Belgian broke that streak in Doha this year.
Former men's world number one Lleyton Hewitt, now at 46 in the world and playing his 14th Roland Garros, was beaten 3-6, 6-2, 6-1, 6-4 by unseeded Argentine Carlos Berlocq.
Hewitt unleashed 56 winners but committed 53 unforced errors.
His fellow Australian Bernard Tomic, now down at 80 in the world, takes on French 12th seed Richard Gasquet who is chasing his 100th career win on clay.
Tomic, the world number 80, has yet to win a main tour claycourt match in 2014.
He had endured a roller-coaster year with a first round, injury-hit exit at the Australian Open followed by double hip surgery and then a 28-minute defeat to Jarkko Nieminen in Miami -- the shortest completed match in history.
German 36-year-old Tommy Haas, the 16th seed, can become the oldest man since Jimmy Connors in 1991 to reach the second round if he defeats Jurgen Zopp of Estonia.
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