Gao Jun was born in Baoding, Hebei province of China. She now resides in Southern California. She is the owner of California Table Tennis club in Rosemead, CA.
She won a silver medal at the 1992 Summer Olympics in the women's double event, with Chen Zihe for the Chinese National Team. She moved to the U.S. in 1994 and became a U.S. citizen. She competed for the United States in three consecutive Olympic Games from 2000 to 2008. In 2009, Gao was inducted into the USATT Hall of Fame.
Gao is a nine-time U.S. women's champion. She also has won eleven U.S. national titles in women's doubles and eight titles in mixed doubles with various partners. She was ranked number 1 in the U.S. prior to the 2012 London Olympics but pulled out of the North American Olympic trials due to an injury.