A　nitrogen　and　phosphorus　co-doped　metal-free　porous　carbon　(NPC)　with　core/shell　structure　was　successfully　synthesized　by　pyrolysis　of　ZIF-8@phytic　acid　(PA)　and　demonstrated　outstanding　catalytic　performance　on　PMS　activation　for　the　degradation　of　phenol　(98.0%　within　30　min　at　pH　=　7.0).　Results　suggested　that　optimized　N-P　co-doping　strategy　played　a　synergistic　effect　in　promoting　the　catalytic　activity　of　NPC.　In　addition,　NPC　displayed　excellent　acid-base　tolerance　(pH　=　3.0–10.0)　and　insensitive　to　anions　(Cl−,　HCO3–　and　H2PO4−)　and　humic　acid　when　employed　as　PMS　activator　for　phenol　degradation.　Based　on　quenching　tests,　electron　paramagnetic　resonance　(EPR)　measurements　and　electrochemical　analysis,　singlet　oxygen　(1O2)　is　the　key　active　specie　and　the　surface-bound　sulfate　radical　(SO4[rad]−)　plays　an　auxiliary　role　in　the　removal　of　phenol　in　NPC/PMS　system　while　surface　electron　transfer　is　also　a　non-radical　pathway.　Large　BET　specific　surface　areas　(SSA),　total　pore　volumes　(TPV)　and　hierarchical　porous　structure　are　beneficial　to　expose　more　active　sites　(essentially　graphite　N　and　C[dbnd]O)　for　generating　1O2　and　surface-bound　SO4[rad]−　to　enhance　catalytic　performance　of　NPC.　This　work　opens　up　a　new　way　for　the　synthesis　of　highly　efficient　N-P　co-doped　metal-free　PMS　activators　and　provides　novel　insights　into　the　mechanism　of　PMS　activation　by　NPC.　©　2021　Elsevier　B.V.