Reversible protonic ceramic cells (RePCCs) hold promise for efficient energy storage, but their practicality is hindered by a lack of high-performance air electrode materials. Ruddlesden–Popper perovskite Sr3Fe2O7-δ (SF) exhibits superior proton uptake and rapid ionic conduction, boosting activity. However, excessive proton uptake during RePCC operation degrades SF’s crystal structure, impacting durability. This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes, incorporating Sr-deficiency and Nb-substitution to create Sr2.8Fe1.8Nb0.2O7-δ (D-SFN). Nb stabilizes SF's crystal, curbing excessive phase formation, and Sr-deficiency boosts oxygen vacancy concentration, optimizing oxygen transport. The D-SFN electrode demonstrates outstanding activity and durability, achieving a peak power density of 596 mW cm-2 in fuel cell mode and a current density of - 1.19 A cm-2 in electrolysis mode at 1.3 V, 650 °C, with excellent cycling durability. This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.