Greenhouse gases emissions, especially CO2, have dramatically increased in the last decades. Hence, concern over the reduction of the rising CO2 atmospheric concentration (above 400 ppm) have led to the development of carbon capture and utilization (CCUs) technologies or carbon capture and storage (CCSs) methods. • For this purpose, designed materials with high carbon dioxide affinity are needed. Previous experimental works reported by our group1 have shown reduction and conversion of carbon dioxide pure gas employing magnesium hydride as hydrogen supplier showing great cobalt catalytic activity. • In this work, Density Functional Theory was applied to comprehend, from an atomistic point of view, the interaction mechanism of carbon dioxide adsorption on magnesium hydride and cobalt catalyzed magnesium hydride systems.