There has been received growing attention to renewable energy sources as a solution of global warming due to release of excess amounts of carbon dioxide into the atmosphere arising from the production and consumption of fossil fuels. The ability to reduce CO2 efficiently by a similar process could also play a role in reducing greenhouse gas emissions and moving us toward a more sustainable economy. CO could be used in chemical production or reacted with H2 to produce liquid fuels via the Fischer-Tropsch reaction. High-temperature solid oxide electrolyzers (SOE) are particularly a favorable technology for the efficient of water electrolysis from electricity because electrolysis at elevated temperatures is advantageous for both thermodynamic and kinetic reasons. We previously reported identification of the layered perovskite materials, such as PrBaMn2O5+δ (PBM) as anode and PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF50) as cathode, with superior electrochemical performance and stability under solid oxide fuel cell operating conditions. In this study, the PBM and PBSCF50 layered perovskite materials employed as a potential ceramic electrodes for use in steam electrolyzer and CO2 SOEC system. The results show that these layered perovskite electrodes are very efficient for hydrogen production and the electrochemical reduction of CO2.