The undesired formation of CH4 during the hydrogenation of CO2 remains a great challenge with direct impact on selectivity towards CO or CH3OH. In this study, the selectivity of a supported Ni catalyst prepared by traditional impregnation method was found to change after a first CO2 hydrogenation reaction cycle from 100 to 800 °C. The usually high CH4 formation was suppressed leading to full selectivity towards CO. This behavior was also observed after the catalyst was treated under methane or propane atmospheres at elevated temperatures. In-situ spectroscopic studies revealed that the accumulation of carbon species on the catalyst surface at high temperature leads to a nickel carbide-like phase. The catalyst regains its high selectivity to CH4 production after carbon depletion from the surface of the Ni particles by oxidation. However, the selectivity readily shifts back towards CO formation after a new temperature programmed CO2 hydrogenation cycle. The fraction of weakly adsorbed CO species increases on the carbide-like surface when compared to a clean nickel surface, explaining the higher selectivity towards CO formation. This easy protocol of changing the surface of a common Ni catalyst to gain selectivity represents an important step for the commercial use of CO2 hydrogenation to CO process together with Fischer-Tropsch applications.