Novel Ni-W-Mg mixed oxide catalysts (NiWMgOx) were prepared by homogeneous precipitation and attempted for the methanation of CO2. Adding W remarkably promoted the activity with improved stability, anti-CO-poisoning ability and resistance against coke formation compared to the undoped NiMgOx catalyst. The superior reactivity of monodentate formate towards hydrogenation than that of bidentate formate species was identified by DRIFTS analysis and the formation of more active monodentate formate species was indisputably facilitated by W additives, leading to the greatly enhanced catalytic activity. H-2-TPR and CO2-TPD characterization showed that doping W increased the number of stable CO2 adsorption sites and helped in anchoring the Ni sites as a result of strengthened Ni-Mg interaction, both of which were responsible for the enhanced CO2 methanation activity and the improved resistance against sintering. (C) 2016 Elsevier B.V. All rights reserved.