In the present work, nano-sized powders of (1-x)Ce0.8Sm0.2O2-delta-xBaCe(0.8)Sm(0.2)O(3-delta) (x = 0, 0.3, 0.5, 0.7 and 1) were obtained by solution combustion synthesis (self-combustion synthesis, SCS) method of nitrate and various types of organic fuels (glycine, glycerin, citric acid and a mixture of citric acid and ethylene glycol). The research results indicate that the finest powders by using the SCS process are formed when the perovskite concentration is decreased in the system under study, as well as when as the fuel glycerin or a mixture of citric acid and ethylene glycol are used. The use of the specific method allows the preparation of dense composite ceramics at 1500 degrees C. The investigation of the electrical properties of the composites at a wide range of temperatures and oxygen partial pressures shows that 0.5Ce(0.8)Sm(0.2)O(0.2-delta)-0.5BaCe(0.8)Sm(0.2)O(3-delta) material is characterized by relatively good stability against CO2, acceptable value of total conductivity and the lowest contribution of electron conductivity in both oxidizing and reducing atmospheres. (C) 2012 Elsevier B.V. All rights reserved.