SrNb0.1Co0.9O3−δ (SNC) perovskite oxide has been prepared by high-energy ball milling followed by calcination at 1100°C. According to oxygen temperature-programmed desorption and thermogravimetry analysis results, highly charged Nb5+ successfully stabilizes the perovskite structure to avoid order-disorder phase transition. The electrical conductivity reaches 550Scm−1 at 300°C in air and as high as 106Scm−1 under P(O2)=1×10−5atm at 900°C. The high electrical conductivity is beneficial in improving the charge-transfer process for the oxygen reduction reaction on the cathode. Based on the defect chemical analysis, the Nb-doping in SrCoO3−δ perovskite facilitates the formation of Co2+, which increases oxygen nonstoichiometry and, subsequently, the mixed valence of [Co2+]/[Co3+] under lower oxygen partial pressure. A relatively low thermal expansion coefficient of 19.1×10−6K−1 in air was achieved. All above properties show SNC to be a promising cathode material in the practical application of low-temperature solid oxide fuel cells.