Twenty mol% gadolinium doped ceria powders were prepared by citrate-nitrate combustion synthesis technique. Two different sources of cerium viz. cerium nitrate and ammonium ceric nitrate were used in different oxidant-to-fuel ratios. The crystallite size of the synthesized powders ranged 5–27nm was obtained depending on the preparation conditions with average particle size in the range 0.64–1.26 mm. Although, the powders were found to be agglomerated in nature, these powders were highly sinter-active as they showed very high sintered density (≥95%) when sintered at 1250 °C having grain size in the range of 200–500 nm. The electrical conductivity was found to depend on the temperature with tw°o distinct regimes at a transition point of 350 °C. The grain boundary showed a significant role in the total conductivity with its activation energy dependent on the material preparation conditions. The activation energy of total conduction was found to be significantly low (~0.5 eV) in the temperature range of 400–700 °C, this property is unique for application as an electrolyte for solid oxide fuel cell operating in the low temperature range. It was found that a fuel-deficient combustion reaction using cerium nitrate as the oxidant yielded the best quality powder which showed a maximum electrical conductivity of ~1 74×10⁻² S/cm at 600 °C.