Display omitted •The introduced Mn on Fe2O3 improved the interfacialconductivity and adsorption.•The kinetic degradation rate of BPA was increased by 235 times through Mn-Fe2O3.•Surface active complexes, O2− and 1O2 were the main reactive species.•Mn-Fe2O3 could operate continuously in the reactor for 23 days. Intrinsically inferior electron transfer rate between catalyst and oxidant was considered as a limiting factor to inhibit the catalytic efficiency of peroxymonosulfate (PMS). In this work, the introduction of Mn atoms into iron oxide (Fe2O3) (Mn-Fe2O3) effectively altered the electronic structure of catalyst surface and promoted the adsorption of PMS, which increased the removal rate of Bisphenol A (BPA) by 235 times, with an extensive pH range (3–11). The main active species contained surface active complexes, superoxide radical (O2−), and singlet oxygen (1O2). The reactor unit could operate continuously for 23 days and still maintain a removal rate of more than 95%. In addition, it had good adaptability to actual water bodies and could effectively reduce the toxicity of BPA. This work shed new light on the regulation of the interfacial electron transfer process between catalyst and oxidant.