Use of perovskite as a cathode for solid oxide electrolysis cell is limited by its insufficient electrolysis current density or catalytic activity. Most of present perovskites used has a crucial drawback - significant segregation of A-site cations (i.e. SrO), likely resulting in the degradation of performance. In this work, spinel oxide of CuFe2O4, which is an alkline earth metal free oxide, is applied as the cathode material to investigate its electrochemical performance, microstructure and chemical composition in the electrolysis of CO2/H2O, steam and CO2. It was found that the exsolution of Cu nanoparticles was observed in CO2/H2O co-electrolysis and the microstructure of CuFe2O4 influenced significantly by operating in different CO2/H2O compositions. Despite the significantly microstructural variation of the CuFe2O4 layer, the cell performs relatively stable electrochemical performance in CO2/H2O and steam electrolysis.