Utilizing polystyrene (PS) microspheres as templates, and graphene oxide (GO) and tetrabutyl titanate (TBT) as raw materials, 3D hierarchical pore rGO/TiO₂(PS) composites were fabricated by Sol-Gel method based on multiple coordination reactions. The structure and morphology of 3D hierarchical pore rGO/TiO₂(PS) composites were characterized, and the effects of PS addition on crystal structure, microscopic morphology and photocatalytic performance of rGO/TiO₂ composites were studied. Under simulate ultraviolet light and visible light irradiation, tetracycline hydrochloride (TTCH) using as the target pollutant, the photocatalytic performance of 3D hierarchical pore rGO/TiO₂(PS) composites prepared with different PS addition was evaluated. Under simulated visible light irradiation, the 3D hierarchical pore rGO/TiO₂(5wt%PS) composites were subjected to multiple recycling tests. The results show that the rGO/TiO₂(PS) composites have a 3D hierarchical pore bulk structure. As the reinforcing phase of matrix, GO keeps stability of multistage pore rigid skeleton structure through Ti-O-C bond. Furthermore, the introduction of PS increases the specific surface area of the rGO/TiO₂(PS) composites. The 3D hierarchical pore rGO/TiO₂(7wt%PS) composite has the highest adsorption efficiency for TTCH, while the 3D hierarchical pore rGO/TiO₂(5wt%PS) composite has the highest photocatalytic activity and stability, which photocatalytic efficiency still reaches 81.02% after 4 cycles of recycling tests; the best addition amount of template PS is 5wt%.