In this paper we report the successful incorporation of high valence transition metals, i.e. Cr, Mo, W, V, Nb, Ti, Zr into SrFeO3−δ perovskite materials, for potential applications as symmetric electrode materials for Solid Oxide Fuel Cells. It is observed that the doping leads to a change from an orthorhombic structure (with partial ordering of oxygen vacancies) to a cubic one (with the oxygen vacancies disordered). These electrodes are chemically compatibles with Ce0.9Gd0.1O1.95 (CGO) and La0.8Sr0.2Ga0.8Mg0.2O3−δ (LSGM) electrolytes at least up to 1100 °C. Thermal annealing experiments in 5% H2–Ar at 800 °C also show the stability of the doped samples in reducing conditions, suggesting that they may be suitable for both cathode and anode applications. In contrast, reduction of undoped SrFeO3−δ leads to the observation of extra peaks indicating the formation of the brownmillerite structure with the associated oxygen vacancy ordering. The performance of these electrodes was examined on dense electrolyte pellets of CGO and LSGM in air and 5% H2–Ar. In both atmospheres an improvement in the area specific resistances (ASR) values is observed for the doped samples with respect to the parent compound. Thus, the results show that high valence transition metals can be incorporated into SrFeO3−δ-based materials and can have a beneficial effect on the electrochemical performance, making them potentially suitable for use as cathode and anode materials in symmetrical SOFC.