At that time, there was a Lao (獠) rebellion in Yong (邕州, roughly modern Nanning, Guangxi) and Yan (巖州, roughly modern Laibin, Guangxi) Prefectures, and Emperor Gaozong launched an army to suppress it, with Li Jiao serving as the army's auditor.
That year, her secret police official Lai Junchen had falsely accused the chancellors Ren Zhigu, Di Renjie, and Pei Xingben, along with other officials Cui Xuanli (崔宣禮), Lu Xian (盧獻), Wei Yuanzhong, and Li Sizhen (李嗣真) of treason.
As a result, they offended Wu Zetian, and she demoted him to be the military advisor to the prefect of Run Prefecture (潤州, roughly modern Zhenjiang, Jiangsu).
While serving in that office, in 697, when Eastern Tujue's khan Ashina Mochuo made a request for Zhou to return Tujue people who had previously submitted to Tang and also to grant a number of supplies that he needed, Li Jiao lodged an objection against the recommendation of the chancellors Yao Shu and Yang Zaisi to comply, but Wu Zetian still granted Ashina Mochuo's requests.
Li Jiao, believing that the time was insufficient, suggested dividing the empire into 20 circuits so that the censors had smaller areas to review.
As of 698, Li Jiao was serving as Mishu Shaojian (秘書少監), the deputy head of the Palace Library, when he was given the designation Tong Fengge Luantai Pingzhangshi (同鳳閣鸞臺平章事), making him a chancellor de facto.
Later in 704, Li Jiao was made acting Neishi (內史), the head of the legislative bureau and also a post considered one for a chancellor.
Li Jiao then requested to be relieved of Neishi duties, and was given the chancellor designation Tong Fengge Luantai Sanpin (同鳳閣鸞臺三品).
That year, when Emperor Zhongzong's son-in-law Wang Tongjiao (王同皎) was accused of a treasonous plot with Zhang Zhongzhi (張仲之), Zu Yanqing (祖延慶), and Zhou Jing (周璟), of plotting to kill Wu Sansi the Prince of Dejing (Wu Zetian's nephew), the lover of Emperor Zhongzong's powerful wife Empress Wei and then depose Empress Wei, Zhang, while being interrogated, openly accused Empress Wei and Wu Sansi of adultery.
He subsequently marched on the palace, hoping to arrest Li Guo'er, Empress Wei, and Emperor Zhongzong's concubine Consort Shangguan Wan'er.
Also in 708, he was made minister of defense (兵部尚書, Bingbu Shangshu) and remained chancellor with the Tong Zhongshu Menxia Sanpin.
Li Jiao initially remained chancellor after Emperor Ruizong's return to the throne, but about a month later was demoted to be the prefect of Huai Prefecture (懷州, roughly modern Jiaozuo, Henan).
At a later point, Li Jiao was made an advisor to the prefect of Lu Prefecture (廬州, roughly modern Hefei, Anhui), where he died at age 69.