The solid oxide electrolytic cell can use a renewable electricity to convert CO2 into CO for storage. However, it still suffers from the sintering of reactive sites and carbon deposition at cathode. In this work, A-site deficient La0.4Ca0.4Ti0.94Ni0.06O3-δ perovskite cathode with the decoration of a large number of exsolved Ni nanoparticles was prepared by an in-situ exsolution method. Also, a promoter of CeO2 was introduced into the system via different synthetic methods (i.e., doping, impregnation and mechanical mixing) to construct a “cerium oxide-metal-perovskite” three-phase composite cathode material. The results show that the carbon deposition resistance and electrochemical performance of the mechanical mixed modified materials can be improved at 800℃, 70% (in volume) CO2/30%CO and 1.4 V electrolytic voltage. The current density is increased by 3 times and the voltage decay rate is decreased by 58%. Such an improvement is correlated to the increased amount of surface oxygen vacancies and the strengthened CO2 absorption.