Nowadays metal-free persulfate-based advanced oxidation processes (AOPs) have been intensively investigated, however, the catalysts are often too complex to fully consider their application potential. Conventional AOPs usually suffer from severe interference in real water matrix, thus, selective oxidation is practically and scientifically challenging as it could avoid unnecessary inputs of energy and possible secondary pollutants. In this study, a remarkably synergistic effect was achieved when conventional amorphous boron/peroxymonosulfate (Boron/PMS, 0.67 x 10(-2) min(-1)) system was combined with electrolysis (E-Boron/PMS, 1.54 x 10(-2 )min(-1)) to degrade sulfamethoxazole (SMX). Evidenced by selectively quenching tests with kinetic evaluation, electron paramagnetic resonance (EPR), solvent-exchange experiment and electrochemical analysis, the dominated reactive oxygen species in E-Boron/PMS system tended to be O-1(2), instead of the (OH)-O-center dot and SO4 center dot- . Mechanistic study unveiled that O-1(2) was generated via accelerated PMS self-decomposition, triggered by interface alkalization and hydroxyl radicals transfer at the cathode interface. O-1(2) is considered to be selective to the electron-rich organic compounds, thus E-Boron/PMS system was superior to conventional radical-dominated system (Boron/PMS) for SMX removal in the co-presence of common inorganic anions, showing the great merits of selective oxidation in nonradical system. These findings provided new insights into effective and selective oxidation of SMX via EBoron/PMS system, which shed new light on the development of nonradical system.