In this study, a permanganate/redox-mediator system for enhanced transformation of a series of emerging contaminants was evaluated. The presence of various redox-mediators (i.e., 1-hydroxybenzotriazole, N-hydroxyphthalimide, violuric acid, syringaldehyde, vanilin, 4-hydroxycoumarin, and p-coumaric acid) accelerated the degradation of bisphenol A (BPA) by Mn(VII). Since 1-hydroxybenzotriazole (HBT) exhibited the highest reactive ability, it was selected to further investigate the reaction mechanisms and quantify the effects of important reaction parameters on Mn(VII)/redox-mediator reactions with BPA and bisphenol AF (BPAF). Interestingly, not only HBT accelerated the degradation of BPA, but also BPA enhanced the decay of HBT. Evidence for the in-situ formation of HBT• radicals as the active oxidant responsible for accelerated BPA and BPAF degradation was obtained by radical scavenging experiments and 31P NMR spin trapping techniques. The routes for HBT• radicals formation involving Mn(VII) and the electron transfer pathway from BPA/BPAF to HBT• radicals demonstrate the Mn(VII)/HBT system was driven by the electron transfer mechanism. Compared to Mn(VII) alone, the presence of HBT totally inhibited self-coupling of BPA and BPAF and promoted -scission, hydroxylation, ring opening, and decarboxylation reactions. Moreover, Mn(VII)/HBT is also effective in real waters with the order of river water > wastewater treatment plant (WWTP) effluent > deionized water.