Display omitted •Fe3C@NCNTs/GNS is simply obtained by a direct pyrolysis of K4Fe(CN)6.•Fe3C@NCNTs/GNS exhibits excellent performance for Bisphenol A (BPA) degradation.•1O2 and O2− are responsible for BPA removal instead of classical OH and SO4−.•Graphitic carbon framework together with N doping induces the non-radical pathway.•Influences of anions, humic acid, and actual sewages are investigated in detail. Developing novel carbocatalysts with available strategies for peroxymonosulfate (PMS) activation has become a popular topic in environmental remediation and protection fields. Herein, using commercial K4Fe(CN)6 as the precursor, Fe3C@nitrogen-doped carbon nanotubes/graphene nanosheets (Fe3C@NCNTs/GNS) is synthesized by a direct high-temperature pyrolysis. Characterization results prove that Fe3C@NCNTs/GNS has a relatively high graphitization degree and rich nitrogen doping content, which endow it with excellent catalytic efficiency in PMS activation for powerful removal of Bisphenol A (BPA). Influences of catalyst/oxidant dosages, some inorganic anions, humic acid, and practical sewages are investigated in detail. For mechanism studies, it is found that tert-butyl alcohol (TBA)/methanol fails to inhibit BPA degradation, and the primary reactive oxidative species (ROS) are superoxide radical (O2−) and singlet oxygen (1O2). Discussion on the origin of 1O2 confirms that moderate modification of N atoms in graphitic carbon frameworks plays an essential role in inducing the non-radical mechanism. This work will provide new insights for the preparation of high-performance carbocatalysts in PMS activation and exploring critical roles of N-doping during non-radical processes.