At the end of 2002, Li left the national tennis team to study part-time at Huazhong University of Science and Technology (HUST), where she completed her bachelor's degree in journalism in 2009.

Notable individual victories in the course of the year included wins over Flavia Pennetta, Emmanuelle Gagliardi, Maria Elena Camerin, Tamarine Tanasugarn and Yayuk Basuki.

In 2002, she came through qualifying to win her first $75k singles tournament at Midland, United States in February, defeating Laura Granville, Tatiana Perebiynis, and Mashona Washington en route to the title, the 14th of her career.

She began the year with a second-round performance at Gold Coast and a semifinal showing at Hobart, but losing to fellow Chinese player and eventual tournament champion Zheng Jie.

After taking a month off from competition, Li returned at Estoril in late April, defeating Stéphanie Cohen-Aloro, Nicole Pratt, Dally Randriantefy, and then crushing Dinara Safina to reach her second WTA Tour final.

The following week, another highly ranked American player, Jill Craybas, narrowly defeated Li Na in a close three-set first-round match at Beijing.

At the Tier I Pan Pacific Open in Tokyo, Li advanced to the second round, defeating Lilia Osterloh before losing to Samantha Stosur in two sets, converting zero of eleven break points.

She continued her good form at the Miami Open, losing just three games in her first two matches against Tamira Paszek and Katarina Srebotnik, before stunning fourth-seeded Kim Clijsters in three sets.

She then moved onto the green clay of Amelia Island, where she suffered a shock second-round exit, after receiving a first round bye, to former top-20 player Karolina Šprem in straight sets.

33 by the time she entered the Tier II tournament at Antwerp in early February, she nonetheless progressed to the semifinals with back-to-back-to-back straight-sets wins over Russian veteran Elena Likhovtseva, Slovak world No.

She played in the Premier event at Indian Wells, where she defeated Tamarine Tanasugarn, Patty Schnyder, and[Amélie Mauresmo, all in straight sets, to advance to the fourth round, where she lost to eventual champion Vera Zvonareva.

At the 2009 Bank of the West Classic, she lost to Serena Williams in the first round, and at the LA Women's Championships, she withdrew due to injury during her match with Urszula Radwańska of Poland.

Li played in the Sydney International as the eighth seed, making fast work of Australian wildcard Anastasia Rodionova and winning a tough three-set match against Virginie Razzano in the first two rounds.

After receiving byes into the second rounds, she lost in a hardly fought match against Yanina Wickmayer at the Dubai Championships, lucky loser Klára Zakopalová at the Qatar Ladies Open and countrywoman Peng Shuai at Indian Wells.

She won her opening match against Lourdes Domínguez Lino and defeated Jarmila Gajdošová and Gréta Arn in the next two rounds en route to back-to-back semifinals on clay.

Li started her 2012 season in the Hopman Cup with countryman Wu Di, who was also from Hubei province, where she won all three single rubbers against Marion Bartoli, Anabel Medina Garrigues and Jarmila Gajdošová.

Li then participated in the Open GDF Suez in Paris, but retired against Tsvetana Pironkova in the first round of the tournament due to a back injury she sustained during her Fed Cup matches.

Li reached the final of the Italian Open, defeating Iveta Benešová, Chanelle Scheepers and Dominika Cibulková without dropping a set before receiving a walkover from Serena Williams in the semifinals.

She cruised to the final with straight-sets defeats over Mandy Minella, Julia Cohen, Bojana Jovanovski and Peng Shuai, putting her in prime position to claim her seventh WTA title.

She fell over a second time after the Australia Day fireworks break, not only twisting her left ankle once more but also heavily knocking the rear of her head on the court, causing a momentary black-out.

As one of the favourites, Li's quest for a second Grand Slam title began when she played Anabel Medina Garrigues in the opening round of Roland Garros, winning in two sets.

Her struggles on clay continued, however, as she fell victim to Bethanie Mattek-Sands, ranked 67th, in a rain-interrupted second round match – losing in three sets, bringing her disappointing clay-court season to a close.

[36] At the San Diego Open, she notched wins over Lauren Davis and Angelique Kerber before receiving a walkover from Agnieszka Radwańska in the quarterfinals after the Pole pulled out for personal reasons.

She then headed to Beijing to take part in the 2013 China Open as the home crowd favourite, defeating Daniela Hantuchová, Bojana Jovanovski and Sabine Lisicki in straight sets before falling to Petra Kvitová in the quarterfinals.

Seeded first at a Premier Mandatory event for the first time, she received a bye in the first round before registering straight set victories over countrywoman Zheng Jie, Karolína Plíšková and Aleksandra Wozniak en route to a quarterfinal clash with Dominika Cibulková, a rematch of the Australian Open final.

Li defeated Madison Keys, Carla Suárez Navarro and Caroline Wozniacki en route to a semifinal against Dominika Cibulková, who was projected to make her top-ten debut with her previous win over Agnieszka Radwańska.

Li's crosscourt forehand tended to be her favourite shot, hit with great accuracy and pace, although her backhand was said to be the more consistent and reliable groundstroke, both of which she was known to unleash unpredictably to all areas of the court to dictate play.

Although she did not possess an overwhelmingly powerful serve, it was very well placed, earning her aces or unreturnables on occasion, however it often became a liability when she lost confidence under pressure, resulting in many double faults.

[68] Under the tutelage of Carlos Rodríguez, Li adopted more of an all-round game, implementing a forehand with additional topspin[69] and frequent net approaches into her arsenal, as well as improved consistency, mental stability,[70] mobility and coordination.

They met three times in 2011, two of which were at Grand Slams, with Li winning on both occasions, before Azarenka won their third meeting at the 2011 WTA Tour Championships, en route to reaching the final.