Liu, who won both the singles and doubles gold medals at the 1996 Atlanta Olympics, had been appointed China's general head coach while retaining the same position with the men's team, the Xinhua news agency reported.
Kong, who partnered Liu in Atlanta and won the singles gold in Sydney four years later, would be in charge of the women's team, it added.
"My predecessor Shi Zhihao did an extraordinary job," Kong was quoted as saying by the report.
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"Under Shi's reign, the Chinese women's team pocketed all gold medals on offer in two Olympic Games, which set the bar high for me.
"... we are not just eyeing to win more gold medals, but going to make table tennis a more popular sport in China and elsewhere of the world." said Kong.
Liu had no illusions about the challenges ahead but was confident of taking Chinese table tennis to a new high.
"It will be very challenging, for sure," Liu said.
"I'm both confident and determined to create a new era of table tennis alongside with my buddy Kong Linghui in the coming years," said the 37-year-old.
China completed a sweep of all the Olympic table tennis golds at last year's London Games, having swept all four titles in the previous Games at Beijing.
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