Liao Li was from Linyuan County (), Wuling Commandery (), which is located within present-day
Changde,
Hunan. He started his career under the warlord
Liu Bei around 209 after Liu Bei succeeded
Liu Qi as the Governor of
Jing Province. Liu Bei employed Liao Li, who was then below the age of 30, as an assistant officer () and later appointed him as the Administrator of
Changsha Commandery. In 211, when Liu Bei led his troops to
Yi Province (covering present-day
Sichuan and
Chongqing), he left his chief adviser
Zhuge Liang behind to take charge of his territories in Jing Province during his absence. During this time, Liu Bei's ally
Sun Quan sent a representative to meet Zhuge Liang and ask him to recommend
scholar-officials who were well-versed in managing a state. Zhuge Liang replied: "
Pang Tong and Liao Li are talents from Jing Province. They are capable of assisting me in governing a state." In 215, when tensions ran high between Liu Bei and Sun Quan over
a territorial dispute in Jing Province, Sun Quan ordered his general
Lü Meng to lead troops to seize three commanderies in southern Jing Province. During this time, Liao Li abandoned his post at
Changsha Commandery and fled west to
Chengdu, the capital of Yi Province, to join Liu Bei. As Liu Bei highly regarded Liao Li, he did not blame him for losing Changsha and instead reassigned him to serve as the Administrator of Ba Commandery (巴郡; covering parts of present-day
Chongqing). In 219, after Liu Bei
seized control of
Hanzhong Commandery and declared himself King of Hanzhong, he appointed Liao Li as a Palace Attendant (). ==Service under Liu Shan==