In　this　study,　the　boron-doped　iron-carbon　composite　(Fe@B/C-2)　was　prepared　via　a　simple　solvothermal　and　secondary　calcination　process　by　using　iron　metal–organic　frameworks　(Fe-MOFs)　as　precursor.　The　obtained　Fe@B/C-2　possessed　abundant　active　sites　and　low　iron　ion　leaching,　and　exhibited　excellent　performance　on　peroxydisulfate　(PDS)　activation　for　efficient　PFOS　(10　mg/L)　degradation　(94　%)　in　60　min,　with　0.2　g/L　of　catalyst　dosage,　1.0　g/L　of　PDS　dosage　and　at　5.0　of　initial　pH.　The　radical　scavenging　and　electron　paramagnetic　resonance　(EPR)　tests　demonstrated　that　SO4·−　and　·OH　were　the　primary　active　species　during　PFOS　elimination.　Under　the　attack　of　these　species,　PFOS　was　first　transformed　into　PFOA,　followed　by　a　sequential　defluorination　process,　and　lastly　mineralized　into　CO2　and　F−.　Notably,　DFT　results　revealed　that　Fe　species,　-BC3/-BC2O　structures　on　the　carbon　matrix　performed　crucial　roles　in　PDS　activation.　The　extraordinary　catalytic　activity　of　Fe@B/C-2　was　attributable　to　the　synergistic　effects　of　Fe　nanoparticles　and　the　B-doped　on　carbon　matrix.　The　doped　B　not　only　could　activate　the　inert　carbon　skeleton　and　provided　more　catalytic　centers,　but　also　could　accelerate　the　electron　transfer　efficiency,　leading　to　a　boost　in　PDS　decomposition.　©　2023