Cu.ZnO.Al2O3 (CZA) catalysts promoted with alkaline earth oxides (MgO, CaO and BaO) were prepared and tested in the CO2 hydrogenation to methanol. The aging conditions was varied to observe the transformation of the amorphous Georgeite into crystalline Malachite phase. At the standard aging conditions (60 oC and 100 min), only the traditional CZA catalyst and the MgO-promoted catalysts showed highly crystalline Malachite phases. For CaO and BaO promotion, the Malachite phase began to be detected only after prolonged aging times. The precursors that formed the Malachite phases presented higher surface areas and TPR profiles with lower reduction temperatures. The CO2 hydrogenation at 30 bar and 10 h-1 showed increased methanol productivity for the catalysts that formed the Malachite phase, with the difference being more significant at lower temperatures. The MgO-promoted catalysts showed the highest productivity and selectivity to methanol at all temperatures studied, also producing less CO. These results were interpreted in terms of the incorporation of Mg+2 into the lattice to form Magnesian-Zincian-Malachite phase in the precursor, which after calcination and reduction may favour the formation of Cu/MgO interfaces that are highly active for the hydrogenation of the CO molecules formed by RWGS