He hailed from Beidi 北地 (modern Wuzhong 吳忠, Ningxia) and was a commander (xiaowei 校尉) under Niu Fu 牛輔, one of the generals of the usurper Dong Zhuo 董卓. Together with Guo Si 郭汜 and Zhang Ji 張濟 he defated the metropolitan magistrate Zhu Juan 朱儁 in Zhongmou 中牟 and looted the commanderies of Chenliu 陳留 and Yingchuan 潁川.
After the death of the tyrant Dong Zhuo he besieged the capital Chang'an 長安 (modern Xi'an 西安, Shaanxi), plundered the surroundings, and killed the Minister of Education (situ 司徒, see Three Dukes 三公) Wang Yun 王允. He was promoted to chariot-and-horse general (cheji jiangjun 車騎將軍) and given the title of Marquis of Chiyang 池陽侯, and was made metropolitan commandant (sili xiaowei 司隷校尉).
He was then so powerful that was one of the three persons that dominated the court politics, together with Guo Si and Fan Chou 樊稠. Yet the three generals soon began to fight against each other. Li Jue killed Fan Chou, and engaged in street fights in Chang'an against Guo Si. Li Jue took Emperor Xian 漢獻帝 (r. 189-220) as a hostage, declared himself acting as Minister of War (dasima 大司馬), burnt down the imperial palace and looted the whole capital. Shortly later he concluded an armistice with Guo Si and released the emperor, only with the result that the latter wandered helplessly around until he arrived in Anyi 安邑.