Ni nanoparticles were successfully generated from a CaTi1-xNixO3 perovskite structure and the effect of Ni substitution level, in the physicochemical characteristics and hence in its catalytic activity and stability in CO2 methanation reaction was evaluated. Particles were generated by a reduction process, where Ni particles were exsolved to perovskite surface. The samples were characterized by SBET, XRD, XPS, TPR, O2-TPD, CO2-TPD, H2-chemisorption and STEM techniques. CaTi1-xNixO3 perovskites with high Ni substitution level (x = 2 and 3) presented the highest catalytic performance with almost 90 % CH4 selectivity and 65 % CO2 conversion with a low CO selectivity of 3 %. These results could be associated with a higher content of medium basic sites and a higher amount of oxygen vacancies. It was also demonstrated that the exsolution process from a perovskite structure leads to smaller Ni particles than that obtained by the impregnation method. The CaTi0.7Ni0.3O3 catalyst presented good stability during 10 h on time on stream. The stability of the catalyst could be associated with the absence of Ni particle sintering. These results evidenced the potential of these catalysts in the CO2 methanation process.