Metal-air batteries have a much higher theoretical energy density than lithium-ion batteries and are frequently advocated as the solution toward next-generation electrochemical energy storage for applications including electric vehicles or grid energy storage. Optimization of the air catalyst and cathode architecture plays a decisive role in improving the performance of metal-air batteries. Air cathode is the performance-limiting electrode in metal-air batteries because of the sluggish ORR/OER activities of most electrocatalysts. Herein, we develop novel double perovskite oxides and demonstrate their bifunctional electrochemical activity towards the oxygen evolution and reduction reactions. The materials synthesized through sol-gel chemistry were characterized for the physicochemical by various diffraction and spectroscopic techniques and further evaluated for electrochemical characteristics. A vibronic superexchange interaction resulting in a predominant M³⁺-O-M'³⁺ interaction was found to positively impact the electrocatalytic activity by enhancing the current densities and lowering the Tafel slope. The findings of the present study deliver a promising pathway for developing novel earth-abundant electrocatalysts and substantiate their suitability as air-breathing cathodes for metal-air batteries.