Spherical samarium doped ceria (Ce0.8Sm0.2O1.9, SDC) powders having high specific surface area (SSA) were successfully synthesized by carbon-assisted spray pyrolysis (CASP). Saccharides, such as monosaccharides and disaccharides, or organic acids were used as carbon sources. The physical and chemical properties of these powders were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Thermo gravimetry-Differential Thermal Analysis (TG-DTA), and BET. Decarbonized powders obtained by this method exhibit spherical morphologies and nano- and submicron-sizes. The SSA of SDC obtained from CASP was more than seven times higher than that obtained from conventional spray pyrolysis (CSP). The SSA of the decarbonized SDC powders obtained by calcination at 900 °C was estimated to be approximately 70 m2/g by using the BET method. The relative density of SDC obtained from CASP was higher than that obtained from CSP. The relative density of the SDC pellet was highest (96 %) when it was sintered at 1400 °C.