<p>Radical-initiated polymerization offers a low-energy and low-carbon alternative for the removal of organic pollutants, but its environmental applicability remains limited by the lack of efficient radical generation methods under mild and sustainable conditions. This work reports a hydraulically driven piezo-catalytic activation of sodium percarbonate strategy to generate carbonate radicals (CO₃^•–) for the polymerization-based removal of phenolic pollutants from water. A polarized layer competition mechanism is proposed to explain the preferential activation of carbonate species over other precursor molecules, resulting in the preferential generation of CO₃^•–. Two polymerization routes, end-group carboxylation and carbon-bridge cleavage, are identified for bisphenol A (a typical phenolic endocrine disruptor) removal, and their detoxification performance is further validated through zebrafish and wheat bioassays. In contrast to conventional assumptions that hydraulic pressure predominantly drives piezoelectric excitation, the mechanistic investigations suggest that three-phase interactions and high-frequency turbulence provided the primary mechanical energy. The process demonstrates strong matrix tolerance against humic acid and inorganic ions, maintained excellent catalytic stability over repeated cycles, and proves effective across structurally diverse phenolic pollutants. This work introduces a CO₃^•–-driven polymerization mechanism and offers a sustainable alternative for water treatment under complex conditions.</p>