Persulfate-based advanced oxidation technol., due to its high efficiency, controllability, and safety, shows great potential for the deep removal of organic pollution, yet its mineralization efficiency is hindered by the lack of synergy between radical and nonradical pathways.Herein, we present defective carbon nitride (DCN) as a highly efficient peroxymonosulfate (PMS) activation catalyst that couples nonradical aggregation with radical mineralization.The tailored electronic structure of the DCN framework enhances visible-light absorption, photogenerated charge separation, and electron transfer ability due to a built-in elec. field.DCN effectively interacts with PMS to rapidly accumulate pollutants from the bulk solution onto the catalyst surface via an electron-transfer pathway.Simultaneously, the accumulated pollutants undergo in-situ decomposition by .SO-4 radicals formed on the catalyst surface under visible light irradiation, achieving a remarkable 98 % mineralization ratio.The mixed-pathway process demonstrates excellent cyclic stability and environmental robustness.This study introduces a novel strategy to enhance the catalytic oxidation performance of metal-free catalysts by controlling persulfate activation pathways for water decontamination.