Born in Guangdong, Li joined the Chinese national table tennis team in 1990, and won second place at the men's single table tennis competition at the National Cup in China.
Li's performance during his time at the Chinese national team fluctuated wildly, due primarily to switching of tactics. In 1994, Li withdrew from the Chinese national team for health reason, and moved to Hong Kong to join its national table tennis team.
During Li's time on the Hong Kong team, he paired up with Ko Lai Chak as a duo, and achieved legendary status after the duo's silver medal win in Athens. In 2006, the duo won a pair of gold medal in their category at the Asian Games held in Doha. Li himself did not do as well in the solo table tennis discipline, being defeated by fellow Chinese athletes during the semi-final stages.