Herein, we report that Co(II)-doped g-C3N4 can efficiently trigger peracetic acid (PAA) oxidation of various sulfonamides (SAs) in a wide pH range. Quite different from the traditional radical-generating or typical nonradical-involved (i.e., singlet oxygenation and mediated electron transfer) catalytic systems, the PAA activation follows a novel nonradical pathway with unprecedented high-valent cobalt-oxo species [Co(IV)] as the dominant reactive species. Our experiments and density functional theory calculations indicate that the Co atom fixated into the nitrogen pots of g-C3N4 serves as the main active site, enabling dissociation of the adsorbed PAA and conversion of the coordinated Co(II) to Co(IV) via a unique two-electron transfer mechanism. Considering Co(IV) to be highly electrophilic in nature, different substituents (i.e., five-membered and six-membered heterocyclic moieties) on the SAs could affect their nucleophilicity, thus leading to the differences in degradation efficiency and transformation pathway. Also, benefiting from the selective oxidation of Co(IV), the established oxidative system exhibits excellent anti-interference capacity and achieves satisfactory decontamination performance under actual water conditions. This study provides a new nonradical approach to degrade SAs by efficiently activating PAA via heterogeneous cobalt-complexed catalysts.