A novel gel-network-coprecipitation process has been developed to prepare ultrafine Cu/ZnO/Al2O3 catalysts for methanol synthesis from CO2 hydrogenation. It is demonstrated that the gel-network-coprecipitation method can allow the preparation of the ultrafine Cu/ZnO/Al2O3 catalysts by homogeneous coprecipitation of the metal nitrate salts in the gel network formed by gelatin solution, which makes the metallic copper in the reduced catalyst exist in much smaller crystallite size and exhibit a much higher metallic copper-specific surface area. The effect of the gel concentration of gelatin on the structure, morphology and catalytic properties of the Cu/ZnO/Al2O3 catalysts for methanol synthesis from hydrogenation of carbon dioxide was investigated. The Cu/ZnO/Al2O3 catalysts prepared by the gel-network-coprecipitation method exhibit a high catalytic activity and selectivity in CO2 hydrogenation to methanol.