Abstract: The photocatalysts of TiO₂-ZnO composite hollow microspheres were obtained by using Ti(SO₄)₂ and Zn(NO₃)₂ as raw materials through hydrothermal method. The structures and properties of as-prepared TiO₂-ZnO samples were characterized by FTIR, XRD, SEM, UV-Vis diffuse reflection spectrum (UV-Vis DRS), XPS and N₂ adsorption-desorption analysis. Methylene blue (MB), as a photocatalytic degradation target, was used to evaluate the photocatalytic performance of the prepared photocatalysts. The results show that the prepared TiO₂-ZnO photocatalyst has a hollow microsphere structure with a particle size of 1-2 μm and a specific surface area of 30.46 m²/g. The light absorption ability of ZnO is improved by the addition of TiO₂ and reduces the electron hole recombination rate effectively. Under high pressure Hg lamp irradiation, the photocatalytic activity of TiO₂-ZnO composite hollow microspheres is higher than that of pure ZnO, and the TiO₂-ZnO sample with Zn(NO₃)₂:Ti(SO₄)2 molar ratio of 1:0.7 has the best photocatalytic activity among all the samples. The degradation rate of MB can reach 95.8% in 60 min, and the photocatalytic degradation rate of TiO₂-ZnO composite hollow microspheres is 4.3 times that of ZnO.