Abstract: ZnAl-LDHs was prepared by in-situ synthesis method on the surface of γ-Al₂O₃, and then a series Ce/Cu/Zn-Al catalysts were prepared by ordinal wet impregnation method. All the catalysts were characterized by XRD, BET, H₂-TPR and XPS to investigate the effects of calcination temperature on the surface structure of Ce/Cu/Zn-Al catalyst and its catalytic performance in methanol steam reforming. The results showed that calcination temperature mainly influenced the specific surface area of copper, surface oxygen vacancy content and the interaction between Cu and Ce. When the calcination temperature is 500℃, the specific surface area of Cu is larger, the content of oxygen vacancy is higher and the interaction between Cu and Ce is stronger. Therefore, the catalytic activity of the catalysts for methanol steam reforming is the best. When the calcination temperature rises to 700℃, the Cu species mainly exist in the form of stable CuAl₂O₄ spinel, which is not conducive to the reaction of methanol steam reforming, resulting in lower catalytic activity.