Peroxymonosulfate (PMS)-based Fenton-like reactions are widely used for wastewater remediation. Metal-free carbonaceous activators can avoid the secondary pollution caused by metal leaching but often suffer from insufficient activity due to limited active centers and mass transfer barriers. Here, we prepared a series of heteroatom (N, S, F)-doped, highly porous carbonaceous materials (UC-X, X = N, S, F) by pyrolyzing UiO-66 precursors assembled by various organic ligands. Density functional theory calculations showed that the heteroatoms modulated the electronic structures of the carbon plane. UC-X exhibited significantly enhanced PMS activation capability compared with the undoped counterpart, in the efficiency order of UC-N > UC-S > UC-F > UC. UC-N (calcined at 1000°C) showed the best PMS activation, exceeding that of commonly used carbocatalysts. The prominent performance of UC-N originated from its unique porous structure and homogeneously dispersed graphitic N moieties. Trapping experiments and electron spin resonance showed a nonradical degradation pathway in the UC-N/PMS system, through which organics were oxidized by donating electrons to UC-N/PMS* metastable complexes. This work not only reports a universal way to access high-performance, metal-free PMS activators but also provides insight into the underlying mechanism of the carbon-activated PMS process.