In this study, H2O2 and persulfate (PS) were both proved to be heterogeneously catalyzed by the Fe3O4 nano particle supported on coal fly ash for reactive oxidation species (ROS). The two heterogeneous advanced oxidation processes (AOPs) were systematically investigated, and the system with H2O2 exhibited higher reactivity for Bisphenol A (BPA) elimination and total organic carbon (TOC) reduction. The two systems were comprehensively compared in terms of degradation kinetics, transformation way, water matrix species and catalyst stability. Systems with H2O2 and PS can remove 100% and 80.2% of the BPA after 120 min (0.22 mmol/L), respectively([H2O2] = 22 mmol/L, [PS] = 22 mmol/L). The oxidant efficiency in system with H2O2 was obviously higher probably due to the less radical scavenging. A mechanism was proposed that the interface interactions between solid and liquid phase will affect the collision among molecular of oxidants and catalyst, as well as the lifetime of radicals during the their diffusion process. The quenching experiments demonstrated that the primary radical species in two systems were center dot O Hand SO4 center dot-/center dot OH, respectively, thus causing the different BPA degradation pathways and by-products. The catalyst presented good structural stability and relatively low Fe leaching in both systems during the recycle. The valence state transformation from Fe2+ to Fe3+ after the reaction explained the gradual catalytic activity loss. In the tap water and municipal wastewater, the system with PS was less influenced by the real water matrix due to the lower university of SO4 center dot- toward organics.