Dynamic Surface Reconfiguration via Dual‐Vacancies Enables High‐Efficiency Photoelectrochemical Catalysis for Photo‐Enhanced Zinc‐Air Batteries

Comprehensive Summary Photo‐enhanced zinc‐air batteries (PZABs) offer a promising approach to coupling solar energy with electrochemical energy conversion, yet their performance remains limited by rapid charge‐carrier recombination and insufficient light‐harvesting efficiency. Here, we propose a dual‐vacancy engineering strategy for NiCrO‐based oxides to simultaneously introduce oxygen and chromium vacancies (NCOV‐Cr, O). The synergistic effect of these vacancies effectively suppresses carrier recombination, enhances photogenerated electron capture, and promotes the in‐situ formation of highly active nickel oxyhydroxide (NiOOH) phases. This structural modulation strengthens the adsorption and activation of *OH intermediates by 1.5 times, providing a stronger thermodynamic driving force for redox processes. As a result, the NCOV‐Cr, O photocathode achieves excellent multifunctional catalytic activity with an onset potential of 0.95 V for the ORR, and low overpotentials of 255 and 33 mV for the OER and HER, respectively. When integrated into a PZAB, the device delivers an ultralong cycling life exceeding 450 h and a peak power density of 253.9 mW·cm −2 under one‐sun illumination. This work showcases that tailoring vacancy defects which recombine the ligand coordination environment creates novel avenues for boosting catalytic performance.