The anodic films of novel Pb-Ca-Sn-Ce alloy, traditional Pb-Ca-Sn and Pb-Sb alloys formed in sulfuric solution at anodic +0.9 V potential corrosion for 6 h were investigated by means of XPS, XRD methods and AC impedance measurement. The results show that the growth of Pb(Ⅱ) oxide on the new Pb-Ca-Sn-Ce alloy surface is inhibited. The AC impedance measurement shows that resistance of the corrosion layer of novel Pb-Ca-Sn-Ce alloy decreases. It is found that the novel Pb-Ca-Sn-Ce alloy can encourage the development of PbO2 in the scale, and enhance the conductivity of the anodic scale. Hence the deep recycling properties of the battery can be expected better.