The Chinese Table Tennis Association have instead handed the slots to tried and tested Olympic campaigners in reigning champion Li Xiaoxia and world champion Ding Ning, the London silver medallist.
Liu will, however, get the chance to make her Olympic debut in Brazil when she teams up with Li and Ding to defend China's team title after London gold medallist Guo Ye was dropped from the national team due to a spine injury.
Zhang Jike will have the chance to defend his singles title in Rio after being picked alongside world number one Ma Long in the men's competition.
The 28-year-old world number four was preferred to Xu Xin and Fan Zhendong for the Aug. 6-17 tournament despite being below them in the world rankings.
World number three Xu will join Ma and Zhang to defend the team title but teenager Fan, second in the world rankings, missed out on the chance to make his Olympic debut.
World champion Ma missed out on a singles berth at the 2012 Olympics after a brief dip in his ranking, despite having dominated the game for much of the previous two years.
China has swept all four table tennis tournaments at the last two Olympic Games.
