Current prospective in the liquid fuels synthesis is prefiguring a greater integration of eco-friendly technologies based on the use of "non-fossil" hydrogen and CO2. Therefore, a series of MOx@CeO2 catalysts (i.e. M = Cu, Fe and Zn), at different MO-to-CeO2 ratio (ca. 0.2-1.5 wt./wt.), were prepared and performed in the in the CO2 hydrogenation reactions at 20 bar and 200-300 degrees C, (GHSV; 4,400NL center dot kg center dot cat(-1) h(-1)). Depending on catalyst composition, the CO2 conversion proceeds according to a "volcano shaped" profiles, resulting more effective at an optimal value of interfacial area (i.e. theta = 0.25). This also substantiate that the occurrence of structuralelectronic synergistic effects plays a key role in the catalytic properties. The different catalytic pathway of CuZnO@CeO2 and CuFeZnO@CeO2 catalysts prove "dual-sites" and "triple-sites" mechanisms in the CO2 hydrogenation reactions, respectively.