She was selected into national team in 2002 after running 4:10.43 in 1500 m and 14:56.15 in 5000 m in 2001 Chinese National Games. In national team, she was coached by Wang Dexian. In 2002, she won bronze medal in 10,000 m in Busan Asian Games with a time of 31:42.36. In 2003, she came in 7th and broke the World Junior Record (30:31.55) in the memorable race of 10,000m at Saint-Denis World Championships. The record was broken by Linet Masai of Kenya at the 2008 Olympics in Beijing.
Xing won the gold medal in the 10,000 m race in the track and field competition at the 2004 Summer Olympics in Athens, Greece with a time of 30:24.36. She overtook Ethiopian Ejagayehu Dibaba in the final straight to break the monopoly of Ethiopians. In Helsinki, she placed 5th in women's 5000 m (14:43.64) and 4th in women's 10,000 m (30:27.18). Both races were won by Ethopian runners. In October 2005, World bronze medalist in 10,000 m in World Championships, Sun Yingjie tested positive in the drug test. National coach for women's long-distance runners, Wang Dexian was banned from coaching for two years due to Sun's offence. The decision of new coach for Xing was not finalized until August, 2006 when her former coach in Shandong Province, Yin Yanqin was assigned to be her coach.
Her unofficial 1500 m personal best is 4:03.00 created in 2005 Chinese national games. However, the result was then cancelled because her opponent, Liu Qing filed a complaint of being deliberately blocked by Xing when Liu tried overtaking Xing.