Methanol synthesis by the hydrogenation of CO2 over Zn-deposited polycrystalline Cu was studied using surface science techniques. The Zn sub-monolayer was oxidized by the reaction mixture during the reaction at 523 K, leading to the formation of ZnO species. The kinetic results definitely showed that the ZnO species on the Cu surface promoted the catalytic activity of methanol formation, where the activity of Cu increased by a factor of 6 at the Zn coverage of 0.17. A volcano-shaped curve was obtained for the correlation between the Zn coverage and the catalytic activity, which was very similar to the correlation curve between the oxygen coverage and the specific activity for methanol formation previously obtained for the Cu powder catalysts. The role of ZnO in Cu/ZnO based catalysts was ascribed to the stabilization of Cu+ species by the ZnO moieties on the Cu surface.