The MoV0.31Te0.23Nb0.24 mixed oxide (M) catalysts with different cerium amounts for propane ammoxidation to acrylonitrile were synthesized by the co-precipitation method. The effect of cerium content on the physicochemical property of the M catalyst was investigated by low-temperature N2 adsorption, XRD, XPS and H2-TPR. The results show that the presence of cerium in the M catalyst can significantly enhance its catalytic performance for propane ammoxidation. 46% acrylonitrile yield can be obtained over the MCe0.05 catalyst with Ce/Mo=0.05 (mol) at SV of 1200mL/(h.g), in which there are most optimal surface compositions, such as more M1 and M2 active phases, and higher Te4+ concentration and appropriate V content. The presence of Ce3+/Ce4+ pairs promotes the redox capability of the M catalyst and more reasonable atom distribution on the catalyst surface.