BaCe 0.8Sm 0.1Gd 0.1O 3− δ , a material for an electrolyte of solid oxide fuel cells, was prepared by a newly sol-combustion method to obtain fine grain size and good sinterability. The phase formation, sinterability and electrical conductivity were focused on by this study. The results show that nano-sized BaCe 0.8Sm 0.1Gd 0.1O 3− δ powders with single orthorhombic perovskite structure were prepared by this process successfully. The powders showed high sinterability, and a relative of 95.2% of the theoretical density was obtained at a sintering temperature of 1400 °C. Electrochemistry measurements showed that the BaCe 0.8Sm 0.1Gd 0.1O 3− δ ceramics had relatively high oxygen ionic conductivity in low-temperature range.