The hydrogenation of CO2 over a Zn-deposited polycrystalline Cu surface was performed at 523 K and 18 atm using a a high-pressure reactor combined with an XPS-AES apparatus. It was clearly shown that ZnOx species formed on the Cu surface during the reaction directly promoted the methanol formation activity, indicating the creation of active sites except for Cu-0. At optimum Zn coverage (Theta(Zn) = 0.17) the Zn-deposited Cu surface was sixfold more active than the Zn-free Cu surface for methanol formation. The turnover frequencies (TOF) increased with Zn coverage below Theta(Zn) = 0.17 and decreased above Theta(Zn) = 0.17. The TOF and the activation energy for methanol formation over the Zn-deposited Cu were in fairly good agreement with those for the Cu/ZnO powder catalysts. Thus, the Zn-deposited Cu surface can be regarded as a model of Cu/ZnO catalysts. The postreaction surface analysis by XPS, after evacuation of the reaction mixture at 523 K, showed the formation of ZnOx species with a Zn/O ratio of about unity at any Zn coverage. Formate species was observed on the postreaction Cu surface in the presence of the ZnOx species. The amount of the formate species increased with Theta(Zn) below Theta(Zn) = 0.2 and then slightly decreased at Theta(Zn) > 0.2.