Persulfate-based　advanced　oxidation　technology,　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　electric　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　•SO4−　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.　©　2024　Elsevier　B.V.