Li Na, who has taken both the French and Australian Open titles, made the widely expected announcement in a statement on social media.
After four knee surgeries, “my body is begging me to stop the pounding”, Li Na wrote.
The Chinese Tennis Association thanked her for the “shining moments” Li Na had given to the sport.
Li Na is one of China’s most high-profile athletes and a national hero.
She is well-known for her outspoken independence, her humor and her reluctance to embrace the state-run training system.
Li Na won the Australian Open in January to add to her 2011 French Open title, but the world number six has not played since losing in the third round at Wimbledon in June.
In a letter posted on Facebook, Li Na said that making the decision to retire had taken “several agonizing months”.
“Representing China on the tennis court was an extraordinary privilege and a true honor,” she wrote.
“Having the unique opportunity to effectively bring more attention to the sport of tennis in China and all over Asia is something I will cherish forever.
“But in sport, just like in life, all great things must come to an end.”
On China’s microblog service Weibo, tens of thousands of Chinese fans inundated Li Na’s page with positive comments.
Many thanked her for representing the country and wished her well, often using an affectionate term for Li. “Good luck Sister Na!” and “Go Sister Na!” were among the more common comments.
“You once said that all you wanted to do is just play tennis, but in reality because of you, so many people have begun to understand what tennis is really about… I sincerely wish you the best. Thank you for guiding and encouraging us,” said one user.
“She never boasts of her patriotism, because all along she has been quietly doing things for this country that are greater than what you and I have ever done… she has refused to flatter others, but now she has expressed her deepest thoughts. I am deeply moved by her discipline and honesty,” said another user.
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