• Nitrogen-doped carbon nanosheets were synthesized by a one-step pyrolysis method. • The PbO 2 electrode was co-modified by nitrogen-doped carbon nanosheets and Ce. • The enhanced electrochemical mechanism of NCNSs-Ce-PbO 2 electrode was explored. In this study, a novel NCNS-Ce-PbO 2 electrode was prepared by electrodeposition method using the rare earth metal Ce and synthesized nitrogen-doped carbon nanosheets (NCNSs). Various characterization and electrochemical performance tests showed that the NCNS-Ce-PbO 2 electrode possessed a denser surface and smaller grains than other NCNS-PbO 2 and Ce-PbO 2 electrodes, with more active surface sites and thus could generate more hydroxyl radicals. N , N -diethyl-m-toluamide (DEET) was selected as the model contaminant to evaluate the electrochemical performance of the novel NCNS-Ce-PbO 2 electrode. The effects of initial pollutant concentration, current density, electrolyte concentration, and initial pH on the removal rates of DEET and chemical oxygen demand (COD) were investigated. Under optimal conditions, after degradation of 150 min, the removal rate of DEET and COD reached 100% and 80.52%, respectively. GC–MS was used to identify intermediate products in the degradation process. The degradation mechanism and possible degradation pathways of DEET with NCNS-Ce-PbO 2 electrode were discussed. The good stability of the NCNS-Ce-PbO 2 anode was confirmed by accelerated lifetime experiments.