In recent years, the massive consumption of fossil fuels has led to increasingly serious environmental pollution. Solid oxide electrolysis cell (SOEC) has attracted more and more attention because it can efficiently and environmentally convert CO2 into CO and other high value-added chemicals. Electrode materials with excellent performance are crucial to the development of efficient and stable SOEC. La0.7Sr0.3Cr0.5Fe0.5O3-δ(Sto-LSCrF)perovskite oxide has attracted widespread attention due to its excellent oxidation-reduction stability. In order to further improve the performance of Sto-LSCrF fuel electrode materials for CO2 electrolysis, the A-site doping Ce strategy in Sto-LSCrF was adopted to improve the content of mobile oxygen vacancies in Ce-LSCrF, so as to increase its adsorption and activation ability of CO2 and then enhance its electrochemistry properties. At the same time, the phase structure, oxygen vacancies content and CO2 adsorption and desorption capacity of the materials were characterized and analyzed in detail. In addition, the electrochemical performance of Ce-LSCrF was explored. Compared with Sto-LSCrF, Ce-LSCrF fuel electrode not only exhibits higher electrolysis performance, but also shows better constant voltage discharge stability. The enhancement of electrolytic performance is attributed to more mobile oxygen vacancies in Ce-LSCrF lattice that can effectively absorb and activate CO2. These results indicate that Ce-LSCrF is an excellent fuel electrode material for CO2 electrolysis in SOEC.