Photocatalysis is an essential approach for treating tetracycline (TC) contaminants, and photocatalytic materials play a crucial role in this process. TiO₂ is a widely used photocatalyst, its morphology will significantly affect its catalytic performance. Therefore, urchin-like (TiO₂-U), nanoparticle (TiO₂-N) and hollow tubular (TiO₂-T) TiO₂ were prepared by hydrothermal method in this paper. The morphology and structure of the prepared catalysts were analyzed by XRD, SEM, XPS, UV-Vis DRS, N₂ adsorption-desorption and EPR, and their degradation performance of TC were investigated. The results show that TiO₂-U contains the greatest number of defects, and the synergistic effect of cationic and anionic defects narrow the band gap of TiO₂-U, which reveal the best catalytic activity. The degradation rate of TC by TiO₂-U can reach 100% at illumination 60 min. In addition, TiO₂-U has a large specific surface area due to its distinctive urchin-like structure, which is conducive to the adsorption of TC and enhances the degradation efficiency.