CeVO4 microspheres were synthesized by a simple hydrothermal method using glycerine as surfactant. The products were characterized by XRD, SEM, HRTEM, XPS, DRS and PL. The results showed that CeVO4 microspheres were self-assembled with nano-hexahedron, and its absorption edge and energy gap was about 800nm and 1.49eV, respectively. Meanwhile, its photocatalytic property was investigated by the degradation of MB under visible light irradiation, and the highest efficiency of 99% was obtained within 300min.