This study reports the effect of transition metal (TM) substitution on the electrical and optical properties of BaCe0.9Sm0.1O3-delta (BCS). Concentrations of 510 mol % of each of Fe and Co have been doped for the B-site of BCS by citric acid autocombustion method. Powder X-ray diffraction has revealed the formation of an orthorhombic perovskite-type structure. FTIR confirmed a distortion in the lattice upon TM-doping in BCS. Scanning electron microscopy (SEM) images of 1400 C sintered samples have manifested a higher densification in BaCe0.8Sm0.1Co0.1O3-delta (BCSC10) with a grain size similar to 11 m compared to the parent compound BCS (similar to 2 m). Thermogravimetric (TG) analysis showed a water uptake in case of BaCe0.85Sm0.1Co0.05O3-delta (BCSC5), while BaCe0.85Sm0.1Fe0.05O3- delta(BCSF5) did not show a noteworthy uptake of water. TG has also proved that the incorporation of Fe and Co in BCS did not improve the chemical stability in CO2 at elevated temperature. The band gap estimated using Kubelka-Munk model based on the diffuse reflectance data was found to be the lowest for BCSC5 (2.47 eV). However, it increases upon lowering oxygen partial pressure (pO(2)), which was interpreted by a band structure modifications. Among the samples investigated, BCSC10 sintered at 1400 C showed the highest electrical conductivity of 0.02 S cm(-1) in air at 600 C, while its proton mobility appears to be negligible under the investigated humidity atmosphere.