Antibiotic residues lead to serious environment pollution and provoke many health problems. Among all the antibiotics, Tetracycline hydrochloride (TC-HCl) in surface and drinking waters around the world has attracted widespread attention. Large-scale SnO2 with hollow microspheres were synthesized via one-step hydrothermal approach as a high-efficiency photocatalyst to degrade TC-HCl. These synthesized series of SnO2 materials with various molar ratios were characterized by XRD, SEM and EIS in terms of crystal structure, morphology, and electronic resistance. SnO2 hollow microspheres synthesized with SnCl2•2H2O to Na3C6H5O7•2H2O at the molar ratio of 1:4 showed the best photocatalytic degradation activity of TC-HCl under UV light illumination. The high photocatalytic property was considered to be benefit from the unique hollow microstructure, and the updated SnO2 hollow microspheres were good candidates for synthesis of composite photocatalysts in area of photo degradation, such as C3N4-SnO2, etc.