The Ni/ZrO2 catalyst doped with Ca and Ni/ZrO2 were employed in the CO2 methanation, a reaction which will possibly be used for storing intermittent energy in the future. The catalysts were characterized by X-ray photoelectron spectroscopy (XPS, reduction in situ), X-ray diffraction (XRD, reduction in situ and Rietveld refinement), electron paramagnetic resonance (EPR), temperature-programmed surface reaction, cyclohexane dehydrogenation model reaction, temperature-programmed desorption of CO2 and chemical analysis. The catalytic behavior of these catalysts in the CO2 methanation was analyzed employing a conventional catalytic test. Adding Ca to Ni/ZrO2, the metallic surface area did not change whereas the CO2 consumption rate almost tripled. The XRD, XPS and EPR analyses showed that Ca+2 but also some Ni2+ are on the ZrO2 surface lattice of the Ni/CaZrO2 catalyst. These cations form pairs which are composed of oxygen vacancies and coordinatively unsaturated sites (cus). By increasing the number of these pairs, the CO2 methanation rate increases. Moreover, the number of active sites of the CO2 methanation rate limiting step (CO and/or formate species decomposition, rls) is enhanced as well, showing that the rls occurs on the vacancies-cus sites pairs. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.