Oxides with superstructure have attracted special attention for their great tolerance in structure and composition regulation, which enables them to have great potential in energy conversion devices, electromagnetic regulation devices, spintronic devices, and so on. Here, we successfully prepared a superstructure oxide Sr4Fe5CoO13-δ via combustion method. X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectra (XAS) analysis suggest that Co dopant could improve the amount of oxygen vacancies in oxides. Unlike the thermal activated electrical conducting behavior of Sr4Fe6O13-δ, Sr4Fe5CoO13-δ demonstrates an electrical behavior in line with the Mott's variable range hopping (VRH) model at low temperatures, implying the localization of electrons. Sr4Fe5CoO13-δ shows a ferromagnetic property with a high Curie temperature of 771 K, which should be attributed to the new formed Dzyaloshinskii-Moriya (D-M) interaction of Fe–O–Co, the increased lattice distortion and the increased amount of oxygen vacancies induced by Co dopant. These properties render it a broadened working temperature range and may contribute to explore high temperature spintronic devices.