Peroxymonosulfate (PMS) activation based on iron-based catalyst has caught increasing attention in wastewater treatment, but is strongly impeded by the sluggish kinetics of Fe(II) recovery. In this study, nitrogen-doped carbon encapsulated Fe3C with dual-reaction centres coupled via CFe channel was developed by electrospinning and Chemical Vapor Deposition (CVD) technique. The remarkable catalysis performance was conferred by the formation of CFe short bond which linked C poor electron reaction centres from N-doped carbon frameworks and the Fe rich electron reaction centres from Fe3C. Fe@NC-800 achieved 100% sulfamethoxazole (SMX) degradation within 20 min, and showed excellent cycle stability after 5 cycles. The electron transfer rate between the dual-reaction region was accelerated due to short transport distance and low transmission resistance. Electrons from pollutants were compensated to Fe3+ via CFe bond bridges, promoting the regeneration of Fe2+ and accelerating the efficiency of the Fe2+/Fe3+ cycle. Besides, the experiments of reactive oxygen species (ROS) quenching and capture revealed the degradation pathway. Both radical and nonradical oxidation played a key role in the Fe@NC-800/PMS system. This work will offer a valuable clue on the design of multi-benefit catalysts to achieve efficient removal of pollutants in wastewater.