The effect of preparation methods on the structure and catalytic behavior of Cu/ZnO/Al2O3 catalysts for methanol synthesis from hydrogenation of carbon dioxide has been studied, The Cu/ZnO/Al2O3 ultrafine catalysts obtained by a novel gel-coprecipitation process exhibited higher catalytic activity for the synthesis of methanol from CO2 + H-2, The results showed that isomorphous substitution took place between copper and zinc in the precipitates prepared by the novel process. Preparation methods have a significant influence on the structure of the catalyst and catalytic activity for methanol synthesis from hydrogenation of carbon dioxide.