Li Jue became one of Dong Zhuo's high-ranking generals, defending Sishui Gate against the anti-Dong Zhuo coalition led by Yuan Shao and Sun Jian. He was forced to retreat after his general Hua Xiong, the general in charge of the troops at the gate itself, was killed by Guan Yu. Li Jue fought at the Battle of Hulao Gate in the city of Luoyang, protecting Dong Zhuo as he retreated, and he followed him to the new capital of Chang'an. When Dong Zhuo was slain by Wang Yun and Lu Bu, Li Jue allied with fellow generals Guo Si, Fan Chou, Niu Fu, Wang Fang, and Li Meng and recaptured the capital, slaying Wang Yun and countless others. They used Emperor Xian of Han, becoming regents to him. Li Jue had the emperor promote him to commander-in-chief and General of Chariots and Cavalry, and he repelled numerous attacks on the capital to free the emperor. Li Jue defeated an attack on the capital by Ma Teng and Han Sui, but in 196 AD, his colleague Yang Biao plotted to make Cao Cao the new regent for Emperor Xian. He made it seem that Guo Si's wife was having an affair with Li Jue, dividing the two of them. Guo Si's men burnt down the imperial palace and killed several of the emperor's attendants, but Zhang Ji brokered peace between them.
Li Jue escaped the capital with the Emperor soon after, planning to escort him to a new capital. Guo Si executed the two gate guards for letting them pass, as he had planned to outwit Zhang Ji. Later, Yang Feng and Han Xian freed the Emperor from Li Jue's clutches, and Li Jue and Guo Si planned to seize the emperor before he could escape east of the Huashan Mountains and call for an alliance against them. They failed to capture him, and soon, Cao Cao and Xiahou Dun joined the emperor. Li Jue and Guo Si's army was defeated by them, and Han Xian and Yang Feng were defeated when they tried to recapture the emperor from Cao Cao. Li Jue and Guo Si were holed up in their capital of Chang'an, and shortly after the fall of Shouchun in 198 AD, Li Jue was slain by Duan Wei while Guo Si was killed by Wu Xi. Their heads were given to Cao Cao, who awarded the assassins with high ranks.