It　is　critical　to　design　and　synthesize　superior　metal-free　PMS　catalysts,　particularly　to　optimize　the　interaction　between　non-metallic　heteroatoms　and　biochar,　facilitating　electron　conduction　and　the　generation　of　reactive　oxygen　species.　Hence,　this　work　presented　a　feasible　synthetic　strategy　for　anchoring　phosphorus　on　in-situ　nitrogen-doped　biochar　via　ball　milling　at　room　temperature.　Mechanical　forces　triggered　the　dehydration　reaction　between　phosphoric　acid　and　C-OH　bonds,　forming　C[sbnd]O[sbnd]P　bonds.　In　particular,　the　obtained　N　and　P　co-doped　biochar　(NPB)　showed　excellent　catalytic　activity.　The　reaction　and　removal　rate　of　diclofenac　sodium　(DS)　in　the　NPB/PMS　system　were　0.3974　min−1　and　90.08　%　(only　10　min),　respectively,　significantly　higher　than　those　in　the　in-situ　nitrogen-doped　biochar/PMS　system.　The　impressive　catalytic　efficiency　was　attributed　to　the　coupling　effect　of　high-efficiency　adsorption　and　exceptional　electron　transfer　capabilities.　Anchoring　P　into　the　carbon　structure　effectively　expedited　the　electron　transfer　from　adsorbed　DS　molecules　to　metastable　PMS　complexes　via　the　carbon-bridge　effect,　ultimately　leading　to　DS　degradation.　The　C[dbnd]O　groups,　pyridinic　N,　graphitic　N,　and　defect　sites　were　possible　active　sites　for　PMS　activation.　GC/MS　identified　the　potential　degradation　paths　of　DS,　but　the　toxicity　of　DS　and　its　intermediates　was　noteworthy.　Furthermore,　the　DS　degradation　efficiency　of　the　NPB/PMS　system　was　little　hampered　by　pH　(2.95–9.07),　anions,　humic　acid,　and　actual　water,　suggesting　its　application　potential　in　real-world　wastewater.　Overall,　this　study　paves　a　new　way　for　constructing　effective　N　and　P　co-doped　non-metallic　PMS　catalysts,　which　may　be　expanded　to　other　carbon　materials　to　fulfil　the　unique　demands　of　various　applications.　©　2022　Elsevier　B.V.