Perovskite compounds in the system of SrCo 1−x Fe x O 3−δ (x=0.2, 0.4 and 0.6) were synthesized by solid state reaction. SrCo 1−x Fe x O 3−δ shows the p-type small polaron conduction behavior. Electrical conductivity and oxygen vacancy content decrease with increase in Fe content. The incorporation of Fe increases the structural stability of SrCo 1−x Fe x O 3−δ at low temperatures, while decreasing the structural stability at high temperatures. Oxygen partial pressure has a strong influence on electrical conductivity. At low oxygen partial pressure, SrCo 0.8 Fe 0.2 O 3−δ will transform from cubic to orthorhombic structure. This structure can remain in 5%H 2 /Ar only for a short time and then dissociates into Sr 3 Fe 2 O 6.64 and Co due to the reduction of B-site elements.