Abstract: Cr/Cu-Ce catalyts with different Cr contents were prepared by impregnation method, and their structures, properties and catalytic performance were investigated using N₂O titration, H₂-TPR and XPS techniques. It is found that the Cr doping changs the specific surface area of copper, the reduction temperature of CuO and oxygen vacancies of the Cu-Ce catalysts. In addition, the catalyst with 3% Cr addition has larger Cu specific surface area, lower CuO reduction temperature and more oxygen vacancies, thus exhibits excellent catalytic performance. The catalytic efficiency reaches 100% and CO volume fraction in outlet gas is 0.15% when the reaction temperature is 533 K, n(water):n(methanol) is 1.2:1 and the feeding rate of methanol and water is 0.072 mL/min. Compared with the un-doped Cr catalyst, the catalytic efficiency increases by 10% and the volume fraction of CO in the outlet gas decreases by 0.34%.