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The aqueous photodegradation of bisphenol A (BPA) in the presence of Fe(Ⅲ)-oxalate complexes (Fe(Ⅲ)-Ox), which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe(Ⅲ)-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial processes of Fe(Ⅲ)-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance (ESR) methods with the steady-state concentration of 2.56 × 10-14 mol/L. Superoxide anion radical (O2.-) was consistructural analysis of the intermediate photoproducts of BPA in Fe(Ⅲ)-Ox complexes solution, the possible degradation pathways of of Fe(Ⅲ) may affect the environmental fate of BPA in natural water significantly.