AbstractTransition metal oxides are promising electrocatalysts for zinc-air batteries, yet surface reconstruction caused by the adsorbate evolution mechanism, which induces zinc-ion battery behavior in the oxygen evolution reaction, leads to poor cycling performance. In this study, we propose a lattice oxygen mechanism involving proton acceptors to overcome the poor performance of the battery in the OER process. We introduce a stable solid base, hydroxy BaCaSiO₄, onto the surfaces of PrBa_0.5Ca_0.5Co₂O_5+δ perovskite nanofibers with a one-step exsolution strategy. The HO-Si sites on the hydroxy BaCaSiO₄ significantly accelerate proton transfer from the OH* adsorbed on PrBa_0.5Ca_0.5Co₂O_5+δ during the OER process. As a proof of concept, a rechargeable zinc-air battery assembled with this composite electrocatalyst is stable in an alkaline environment for over 150 hours at 5 mA cm^–2 during galvanostatic charge/discharge tests. Our findings open new avenues for designing efficient OER electrocatalysts for rechargeable zinc-air batteries.