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　NP　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　(O-1(2))　is　the　key　active　specie　and　the　surface-bound　sulfate　radical　(SO4　center　dot-)　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=O)　for　generating　O-1(2)　and　surface-bound　SO4　center　dot-　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.