As　the　cheap　and　efficient　catalysts,　the　iron-based　catalysts　have　been　considered　as　one　of　the　most　promising　catalysts　for　peroxydisulfate　(PDS)　activation　and　the　development　of　high-performance　iron-based　catalysts　are　attracting　growing　attentions.　In　this　work,　a　magnetic　Fe-based　catalysts　(Fe/NC-1000)　was　obtained　by　using　Fe　modified　ZIF-8　as　the　precursor　and　used　to　activate　the　PDS　for　the　degradation　of　perfluorooctane　sulphonate　(PFOS).　Morphology　and　structure　analysis　showed　that　the　resulted　Fe/NC-1000　catalyst　was　displayed　porous　spheres　(40–60　nm)　and　mainly　composed　of　Fe0,　FeNx　and　carbon.　When　Fe/NC-1000　was　employed　to　activate　the　PDS　(0.1　g/L　of　catalyst　dosage,　0.5　g/L　of　PDS　dosage　and　at　initial　pH　of　4.6),　the　Fe/NC-1000/PDS　system　exhibited　excellent　efficiency　(97.9　±　0.1)　%　for　PFOS　(10　mg/L)　degradation　within　30　min.　The　quenching　tests　and　EPR　results　revealed　that　the　Fe/NC-1000/PDS　system　degraded　PFOS　primarily　through　singlet　oxygen　(1O2)　evolution　and　electron-transfer　process.　Besides,　based　on　the　degradation　byproducts　determined　by　LC-MS-MS,　the　PFOS　first　occurred　de-sulfonation　to　form　PFOA,　and　then　the　resulted　PFOA　underwent　stepwise　defluorination　in　the　Fe/NC-1000/PDS　system.　Density　Functional　Theory　(DFT)　calculations　and　electrochemistry　tests　strongly　confirmed　that　Fe/NC-1000　exhibited　high　electron　transfer　efficiency,　resulting　in　promoted　performance　on　activating　PDS.　Importantly,　the　results　of　Ecological　Structure-Activity　Relationship　(ECOSAR)　analysis　showed　that　the　intermediates　were　lowly　toxic　during　the　PFOS　degradation,　manifesting　a　green　process　for　PFOS　removal.　This　study　would　provide　more　understandings　for　the　persulfate　activation　process　mediated　by　Fe-based　catalysts　for　Perfluorinated　alkyl　substances　(PFAS)　elimination.　©　2023　The　Authors