The combination of peroxymonosulfate (PMS) and electrolysis with an activated carbon fiber (ACF) as cathode (E-ACF-PMS) was systematically investigated. A synergistic effect was observed in the E-ACF-PMS process. Compared with the E-ACF-PDS process, the E-ACF-PMS process spent one-third as much energy for elimination of carbamazepine (CBZ). Increased PMS concentration, current density, and pH value significantly enhanced CBZ elimination. It was also noted that the presence of phosphate (PO43-), bicarbonate (HCO3-), and humic acid (HA) inhibited CBZ removal, while the presence of chloride ion (Cl-) accelerated it. According to radical scavenging experiments and the estimation of relative contribution, reactive oxygen species oxidation (including OH, SO4•-, and 1O2) played an important role in CBZ degradation, accounting for 75.67%. We systematically explored the production mechanism for 1O2 and the results demonstrated that 1O2 was mainly generated on the cathode, rather than generated by O2•- or O2 reported by other researchers. Possible degradation pathways for CBZ in E-ACF-PMS process were also proposed. Finally, the potential for practical applications was explored and compared with E-ACF-PDS. The results of SEM images, BET, and nitrogen adsorption isotherm before and after ACF reuse for 50 times suggested that ACF could maintain its adsorption capacity and catalytic ability in the E-ACF-PMS process. Testing also suggested that the protection of ACF in electrochemical oxidation was based on its relatively high current intensity and removal efficiency. The removal efficiencies of other organic pollutants, including nitrobenzene (NB), sulfamethoxazole (SMX), diclofenac (DC), and tetracycline (TC) were also evaluated. In addition, experiments were conducted to study the effects of different water matrices and toxicology implications and results demonstrated that substituting PMS for PDS in an E-ACF system could create a more efficient, sustainable, and with less secondary toxicity process for wastewater treatment. Copyright © 2019 Elsevier Ltd. All rights reserved.