Photo‐assisted Zn–air batteries can accelerate the kinetics of oxygen reduction and oxygen evolution reactions (ORR/OER); however, challenges such as rapid charge carrier recombination and continuous electrolyte evaporation remain. Herein, for the first time, piezoelectric catalysis is introduced in a photo‐assisted Zn–air battery to improve carrier separation capability and accelerate the ORR/OER kinetics of the photoelectric cathode. The designed microhelical catalyst exploits simple harmonic vibrations to regenerate the built‐in electric field continuously. Specifically, in the presence of the low‐frequency kinetic energy that occurs during water flow, the piezoelectric–photocoupling catalyst of poly(vinylidene fluoride‐co‐trifluoroethylene)@ferric oxide(Fe@P(V‐T)) is periodically deformed, generating a constant reconfiguration of the built‐in electric field that separates photogenerated electrons and holes continuously. Further, on exposure to microvibrations, the gap between the charge and discharge potentials of the Fe@P(V‐T)‐based photo‐assisted Zn–air battery is reduced by 1.7 times compared to that without piezoelectric assistance, indicating that piezoelectric catalysis is highly effective for enhancing photocatalytic efficiency. This study provides a thorough understanding of coupling piezoelectric polarization and photo‐assisted strategy in the field of energy storage and opens a fresh perspective for the investigation of multi‐field coupling‐assisted Zn–air batteries.