TiO2 hollow microspheres has been successfully synthesized via a solvothermal method using tetrabutyl titanate as precursor. The TiO2 hollow microspheres were characterized and analyzed by X-ray diffraction(XRD),electron microscope scanning (SEM), transmission electron microscope(TEM), and N2 adsorption-desorption. The photocatalytic degradation performance was evaluated under the condition of methyl orange(MO) simulating wastewater. The results showed that TiO2 hollow microspheres were nanometer anatase, which is formation of hollow structure composed of nano crystalline self-assembly. The diameter of the TiO2 hollow microspheres was 0.4~0.5 μm. The TiO2 hollow microspheres has mesoporous structures and a high specific surface area, when the methyl orange solution with 15 mg/L of initial mass concentration under UV light using TiO2 hollow microspheres for 80 min，the degradation rate of methyl orange can reach 95%.