Hydroxyl radicals (·OH) is one of the most important reactive oxygen species (ROSs) for organic pollution controlling in advanced oxidation processes, while its production suffers from numerous HO addition and narrow pH range in generally used Fenton reaction. Herein, we demonstrate a BiOIO (BIO) piezo-catalyst loaded with γ-FeOOH nanoparticles (FNPs) (BF) that can convert O to ·OH in a wide pH condition without external HO addition under ultrasonication. It is found that the robust interfacial interaction facilitates rapid electron migration from BIO to FNPs, enabling two-electron O reduction into HO at the FNPs site, while the leaving behind piezo-holes to perform two-electron water oxidative HO generation on BIO. Because the electron-rich nature of FNPs favors the H adsorption that contributes a surface acidic micro-environment, the produced HO can be in-situ catalyzed into ·OH in either neutral or even alkaline conditions with a great stability. Finally, the optimal BF can achieve either an impressive ·OH yield of 38.1 µM h or a high HO yield of 522.0 µM h by regulating the FNPs loading mass, which enables dual capabilities of rapid organic pollutants degradation and HO production in a wide pH condition.