A novel electro-generated hydroxyl radical (center dot OH) technique was constructed to effectively degrade the anti-epilepsy carbamazepine (CBZ) representing typical recalcitrant pharmaceutical only through electrochemical method as an alterative peroxone process. The technique involves simultaneously electro-generated H2O2 using a carbon-polytetrafluoroethylene (C/PTFE) cathode to reduce the injected O-2 and electro-generated O-3 using H2O oxidation with a Ti mesh/PbO2 anode in membrane electrode assembly (MEA). The significant center dot OH formation through the synergetic system of in-situ produced H2O2 and O-3 electrochemically could achieved carbamazepine decomposition and total organic carbon (TOC) removal as compared to electro-generated H2O2 or O-3 alone. The main influential factors including current density and aqueous pH were investigated to reveal their effect on CBZ removal efficiencies. Under optimal parameters, CBZ decomposition and TOC mineralization could be completely accomplished after 10 min and 90 min electrolysis, respectively. According to intermediates distribution (e.g. hydroxylated CBZ, phenolics, and carboxylic acids) identified by HPLC-MS/MS, the degradation pathways were proposed for CBZ removal by the synergetic system of C/PTFE-O-2 and MEA. The above results indicated that this electrochemically synergetic system is a potential technique to further purify the water contaminated by recalcitrant pharmaceuticals. (C) 2018 Elsevier Ltd. All rights reserved.