A kind of high-efficiency photocatalyst of the three-dimensional flower-like TiO₂/TiOF₂ was synthesized by a one-step hydrothermal method. XRD, FE-SEM, EDS, HTEM, BET, XPS, PL, and UV-Vis-DRS were utilized to characterize the photocatalyst. The photocatalyst of TiO₂/TiOF₂ shows a narrow band gap of 2.8 eV. The generation of Ti³⁺ and an oxygen vacancy (O_v) in the photocatalyst are helpful to increase the absorption of visible light, and to inhibit faster charge recombination by capturing photogenerated carriers. Through the degradation of tetracycline hydrochloride (TCH) under simulated sunlight, the photocatalytic activity and stability of the synthesized samples were investigated. The results showed that the removal rate of tetracycline hydrochloride was 59% only in 0.5 h of dark reaction and 85% in 0.5 h of simulated sunlight. The removal efficiency of the photocatalyst for the adsorption and photocatalytic degradation of TCH is higher than that of the single TiO₂, TiOF₂, and Degussa P25. The synthesized three-dimensional flower-like TiO₂/TiOF₂ has great application potential in the treatment of antibiotic wastewater.