The hydrogenation of CO2 over physically-mixed Cu/SiO2 and ZnO/SiO2 was carried out to clarify the synergetic effect between Cu and ZnO in Cu/ZnO methanol synthesis catalysts. The activity of the physical mixtures significantly increased with increasing reduction temperature in the range of 573-723 K. TEM-EDX results definitely showed that ZnOx moieties migrated from ZnO/SiO2 particles onto the surface of Cu particles when the physical mixtures were reduced at high temperatures above 573 K. Upon the migration of the ZnOx species, the oxygen coverage on the surface of Cu, measured after the hydrogenation of CO2, increased with the reduction temperature. The results clearly showed that the synergetic effect of ZnO in the physical mixtures can be ascribed to the creation of active sites such as Cu+ which the ZnOx moieties stabilize on the Cu surface. Further, XRD results showed that the migrated ZnOx species partly dissolved into the Cu particles to form a Cu-Zn alloy.