Abstract: In this paper, CeO₂ nanomaterials with oxygen vacancies and CuO/CeO₂ catalysts for hydrogen production from methanol steam reforming were prepared by precipitation and impregnation methods.The influence of different calcination atmosphere on the structure and properties of CeO₂ nanomaterials and the hydrogen production performance of methanol steam reforming was investigated.SEM, XRD, BET, H₂-TPR, N₂O titration and XPS were adopted to characterize the catalyst materials.The results showed that the catalytic activity of CuO/CeO₂ catalyst was closely related to the surface area of copper, the strength of Cu-Ce interaction, the number of surface defects and surface oxygen vacancies.When the reaction temperature was 250℃, the molar ratio of water to methanol was 1.2 and the gas hourly space velocity was 800 h^-1, the methanol conversion was 100% and the CO concentration in the offgas was 0.87%.