TiO2 and 10 wt%Ni-ZrxTi1−xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts were synthesized and used for CO2 methanation reaction. The catalyst with 10 mol% Zr addition (10 wt%Ni-Zr0.1Ti0.9O2) exhibited the highest CO2 conversion and CH4 selectivity with highly stable property. The role of Zr addition on enhancing CO2 methanation reaction rate was to tune the electronic property of Ni species by electron transfer from Zr to Ni valence state. From the donating effect of Zr, an appropriate metal-support interaction was then improved which led to higher dispersion of Ni species on catalyst surface which was beneficial to the adsorption of H2 molecules. Moreover, Zr addition also improved the basicity of the catalyst, which can also promote the adsorption of CO2. Therefore, an appropriate H2 and CO2 adsorption ability can enhance catalytic activity. The effect of tuning electronic properties by Zr addition on enhancing the catalytic performance resulted from lowering of C-O bonding dissociation barrier. Upon CO intermediate was adsorbed on Ni electron rich site, the electron of valence d state of Ni was transferred to π* anti-bonding of CO molecule and the C-O bonding was then weakened and easily dissociated to carbon and oxygen to further hydrogenation and formed products.