Transition metal phosphides have shown great potentials in persulfate activation for eliminating organic contaminants, while the understanding of the activation mechanism still remains fragmentary. Herein, a series of nitrogen-phosphorus-doped carbon nanotube-coated cobalt phosphide catalysts (Co/P-CNTs) were synthesized for activating peroxymonosulfate (PMS) to degrade norfloxacin (NOR). The optimal Co/P-CNTs-0.3 could eliminate NOR up to 97 % within 60 min in the presence of PMS. Results confirm that the synergistic interaction between multi-valent Co species in the Co/P-CNTs significantly contributes to the excellent PMS activation performance. The contribution of reactive oxygen species (ROS) to pollutant removal and the steady-state concentration of free radicals were quantitatively analyzed by means of chemical probe and reaction kinetics. A free radical mechanism dominated by SO4•– and NOR degradation pathway were identified, and the effect of coexisting inorganic anions was systematically evaluated. This study offers profound insights into the activation mechanism of metal phosphides towards environmental remediation.