Nitrogen-doped graphenes (NG) fabricated through thermal annealing of graphene oxide (GO) and urea was applied to activate peroxymonosulfate (PMS) for sulfacetamide (SAM) degradation. The contents of reactive functional groups (graphitic N, pyridinic N, pyrrolic N, nitric oxide and Cdouble bondO) and catalytic performance of NG were delicately controlled by adjusting thermal annealing temperature. Thermal annealing temperature of ≥500°C was required to produce the NG endowed with catalytic activity for SAM degradation via PMS activation. NG600 (NG prepared at 600°C) with a high N doping level (16.0 wt%) and a most optimum amount of pyridinic N (38.4%N), pyrrolic N (31.8%N), graphitic N (25.9%N) and Cdouble bondO groups (43.7%O) exhibited the most outstanding catalytic activity to activate PMS. NG600 with the controlled N bonding configurations possessed a higher SAM degradation efficiency than NGs prepared via other optimized synthesis methods The specific surface area (SSA) contributed less significantly than N doping to the SAM degradation performance. Increments in the PMS dosage and catalyst loading were both conducive to the catalytic performance of NG. The presence of NO₃⁻ in the NG600/PMS system had a negligible influence on SAM degradation but Cl⁻ and humic acid decreased the SAM degradation rate. Experiments using chemical scavengers and electron paramagnetic resonance (EPR) study revealed that SAM degradation process follows predominantly the radical pathway with sulfate radical (SO₄radical dot⁻) as the main reactive oxygen species over the non-radical pathway. Density functional theory (DFT) calculations suggest that graphitic N can facilitate PMS adsorption on the NG and SAM degradation. This study improves the understanding on the role of different surface N functional groups of NG in the PMS activation.