Herein, Fe(III)-doped g-C3N4 (FeCN) could efficiently activate peroxymonosulfate (PMS), which was prepared via a facile one-pot synthesis approach. The physical and chemical properties of the samples were characterized by XRD, FTIR, SEM, TEM, XPS, and BET. The FeCN/PMS system displayed high activity in the degradation of several contaminants, including cationic rhodamine B (RhB), anionic methyl orange (MO), and neutral phenol. Compared to SO4·−-based advanced oxidation technology, the FeCN/PMS system is a nonradical process; high-valent iron-oxo species (FeIV = O) and singlet oxygen (1O2) are the primary reactive oxygen species (ROS). The effects of various operational parameters, such as catalyst loading, peroxymonosulfate dosage, substrate concentration, and pH, on the performance of the FeCN6/PMS system were also studied. FeCN6/PMS exhibited acceptable degradation of RhB in the presence of coexisting anions (i.e., Cl−, SO42−, NO3−, and H2PO4−) and natural organic matter (NOM). [ABSTRACT FROM AUTHOR]