The effect of ZnO/SiO2 in a physical mixture of Cu/SiO2 and ZnO/SiO2 on methanol synthesis from CO2 and H-2 was studied to clarify the role of ZnO in Cu/ZnO-based catalysts. An active Cu/SiO2 was prepared by the following procedure : the Cu/SiO2 and ZnO/SiO2 catalysts with a different SiO2 particle size were mixed and reduced with H-2 at 523-723 K, and the Cu/SiO2 was then separated from the mixture using a sieve. The methanol synthesis activity of the Cu/SiO2 catalyst increased with the reduction temperature and was in fairly good agreement with that previously obtained for the physical mixture of Cu/SiO2 and ZnO/SiO2. These results indicated that the active site for methanol synthesis was created on the Cu/SiO2 upon reduction of the physical mixture with H-2. It was also found that ZnO itself had no promotional effect on the methanol synthesis activity except for the role of ZnO to create the active site. The active site created on the Cu/SiO2 catalyst was found not to promote the formation of formate from CO2 and H-2 on the Cu surface based on in situ FT-IR measurements. A special formate species unstable at 523 K with an OCO asymmetric peak at similar to 1585 cm(-1) was considered to be adsorbed on the active site.