A　series　of　boron　and　nitrogen　co-doped　hierarchical　porous　carbon　materials　(BNC)　were　prepared　via　a　facile　one-step　calcination　process,　and　the　catalytic　performance　of　BNC　on　PMS　activation　for　phenol　removal　was　investigated.　BNC-1　exhibited　the　optimal　catalytic　performance　with　a　phenol　degradation　efficiency　of　99.6%　within　30　min.　B,　N　co-doping　strategy　improved　the　specific　surface　areas　(SSA)　and　total　pore　volumes　(TPV)　of　carbon　catalysts,　providing　them　with　abundant　active　sites,　among　which　graphitic　N　and　BC3　were　identified　as　critical　catalytic　sites　for　PMS　activation.　Quenching　tests,　electron　paramagnetic　resonance　(EPR)　and　electrochemical　experiments　demonstrated　that　singlet　oxygen　(1O2)　was　the　dominant　active　species　while　surface-bound　sulfate　radical　(SO4·-)　played　an　inferior　role　in　the　BNC-1/PMS/Phenol　system,　and　the　role　of　hydroxyl　radical　(·OH),　superoxide　radical　(O2·-)　and　surface　electron　transport　cannot　be　ignored　either.　The　coexistence　of　radical　and　non-radical　oxidation　processes　made　BNC-1/PMS　system　have　excellent　acid-base　tolerance　(pH=3-11),　anti-interference　ability　and　pollutant　mineralization　performance　(68.3%　of　TOC　removal　within　30　min).　This　study　presented　a　high-efficiency　and　environment-friendly　B,　N　co-doped　metal-free　catalyst　for　pollutants　degradation　via　PMS　activation　and　provided　an　in-depth　research　for　the　mechanism　of　PMS　activation　by　BNC.　©　2022　Elsevier　Ltd.