Liu, who won the singles and doubles gold medals at the 1996 Atlanta Olympics, is taking a job as vice-chairman of the China Table Tennis Association, the Xinhua news agency reported, citing the association.
He was appointed to coach the national men's team at the age of 27 years old in 2003 and handed over to Qin Zhijian in April.
China dominates the world in table tennis, winning 28 out of 32 gold medals awarded since table tennis became an Olympics sport in 1988.
Xinhua said the restructuring was to improve training and efficiency in preparation for the 2020 Olympic Games in Tokyo. The men's and women's national teams would be managed separately in future, it said.
Liu's former table tennis partner and fellow national women's team coach, Kong Linghui was suspended in May after a Singaporean hotel sued him over a gambling debt.
(Reporting by Brenda Goh; Editing by Louise Ireland)
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