This study reports new gallium-promoted copper-based catalysts prepared by co-impregnation of methoxide-acetylacetonate (acac) precursors from methanolic solutions onto silica and zinc oxide supports. Catalyst performance in the CO2 hydrogenation to methanol was investigated at 2 MPa and temperatures between 523 and 543 K. A high activity and selectivity for ZnO-supported catalysts was found, which also showed a high stability in terms of both activity and selectivity. The maximum value for the activity was 378 g MeOH/kg cat h at 543 K, with a selectivity of 88% towards methanol production. The high performance of these materials in the CO2 hydrogenation is related to the presence of Ga2O3 promoter and highly dispersed Cu+ species on the surface, determined by XPS and Auger on used catalysts.