Li Na was born on 26 February 1982 in Wuhan, China. At six she followed her father, Li Shengpeng, into badminton, but coaches soon decided that her swing belonged on a tennis court, and at about eight (sources give ages from seven to nine) she was switched to tennis by Xia Xiyao of the Wuhan youth tennis club, against her own wishes. Her father died when she was 14, as she was taking her first steps on the circuit, and she later said that tennis then became her only chance.

She stepped away from the game from 2002 to 2004 and came back stronger. In 2004 she became the first Chinese woman to win a WTA title, in Guangzhou, and in 2006 the first to reach a major quarterfinal, at Wimbledon, and the first to break into the top 10. At the 2011 Australian Open she became the first player representing an Asian country to reach a major singles final, saving a match point against world No. 1 Caroline Wozniacki in the semifinal. Four months later she won the French Open, beating the defending champion Francesca Schiavone in the final, the first major singles title for a player from Asia, man or woman. An estimated 116 million people in China watched.

After a dip following that win, she replaced her husband, Jiang Shan, as her coach with Carlos Rodríguez, Justine Henin's former coach. In 2013 she reached the US Open semifinals and the final of the season-ending championships and finished the year ranked No. 3. In January 2014 she won the Australian Open, beating Dominika Cibulková, after losing two finals there, and she reached a career high of No. 2.

Knee injuries forced her to retire in September 2014, at 32 and as the reigning Australian Open champion; her body, she said, was begging her to stop. She won nine titles, and her success helped make China a major tennis power, with a WTA tournament created in her home city of Wuhan. In 2019 she became the first Asian player inducted into the International Tennis Hall of Fame.