The 2011 French Open champion was named in the women's singles and doubles in an entry list released by the International Tennis Federation on Tuesday.
Li's team told local media earlier this month that she hoped to focus only on the singles given her injuries, regardless of Chinese sports officials' wishes to have her play in both tournaments.
"If it were true, I don't know why they wanted me to play doubles," Li, who was named to partner Zhang Shuai in the doubles, said when asked about her selection.
"Last time I played doubles was during the 2007 Australian Open.
"So far I have not heard from anyone asking me to play doubles," she added.
"I hope they could respect athletes more ... the way they handled this makes me uncomfortable."
Li's 23-year-old partner Zhang failed to qualify for the ongoing Wimbledon's singles and was tipped out of the doubles in the first round.
"I am not 13-years-old and need a guardian," the outspoken Li fumed.
"I am 30 now and all these issues could have been put on the table. If both (parties) are okay, we do it, otherwise we do not."
Li, whose French Open triumph last year made her the first player from an Asian country to win a grand slam tournament, tumbled out of Wimbledon with a second round loss to Romania's Sorana Cirstea on Wednesday.
Li has long had a testy relationship with Chinese officialdom since she publicly criticised the national team's heavy-handed system in 2005.
After clashing with the Chinese Tennis Association over training routines and pay, Li and a handful of other top Chinese women were permitted to break away from the country's Soviet-style sports regime in 2009 to organise their own coaches and touring - and retain most of their prize-money.
Defying officials over the Olympics, however, would be dimly viewed in her home country of 1.3 billion, and Li said she had obliged herself to "obey" the decision with it already taken out of her hands.
"Life is like a cup of tea. It won't be bitter for a life-time but for a short while anyway," she said, striking a more philosophical tone in a message posted on Weibo, the Chinese equivalent of Twitter, where she boasts 5.6 million followers.