Abstract The phase composition and electroconduction in air of solid electrolytes (Ce0.8Sm0.2)1 - xCuxO2 - d (CSCu), where x = 0, 2, 5, 10, and 20 mol % and which are synthesized using the ceramic technology, are studied. Adding an additive of CuO lowers the CSCu sintering temperature by 100– 200°C and leads to the formation of single-phase solid solutions of a fluorite type up to x = 10 mol %. The electroconductivity of the CSCu electrolytes remains practically invariant upon adding up to 5 mol % Cu and equals 0.089–0.095 and 0.017–0.021 S cm-1 at 800 and 600°C. The sintering, adhesion, and electroconductance of composite cathodes based on La0.8Sr0.2MnO3 with 40% CSCu and their electrochemical behavior in air in the temperature interval 900–1000°C on carrying electrolyte Zr0.9Y0.1O1.95 with a CSCu sublayer containing 2 mol % Cu are studied. [ABSTRACT FROM AUTHOR]