Peroxymonosulfate　(PMS)-assisted　photocatalytic　processes　are　economical　and　green　strategies　for　the　treatment　of　pesticide　pollution.　However,　its　degradation　efficiency　is　severely　hindered　by　the　sluggish　kinetics　of　active　centers　regeneration　and　low　charge-transfer.　Herein,　S-scheme　Bi2Fe4O9/BiOBr　heterogeneous　material　was　designed　to　activate　PMS　for　thiabendazole　(TBZ)　degradation.　Bi2Fe4O9　and　BiOBr　have　similar　structural　unit　of　[Bi2O2]2+　to　share　the　Bi-O　bonds,　which　is　favorable　to　form　asymmetric　interface　and　enhance　the　polarization.　Based　on　these　unique　characteristics　between　Bi2Fe4O9　and　BiOBr,　a　robust　internal　electric　field　in　the　S-scheme　heterojunction　is　built,　which　could　provide　driving　force　to　boost　the　electron-transfer　process　and　encourage　the　sustainable　regeneration　of　Fe2+.　After　optimizing　the　proportion　of　Bi2Fe4O9　on　the　composite,　it　was　found　that　50　wt%　Bi2Fe4O9/BiOBr　(BFB-50)　exhibits　the　best　TBZ　removal　efficiency　after　30　min　visible　light　irradiation,　which　is　2.25　and　12　folds　compared　to　Bi2Fe4O9　and　BiOBr,　respectively.　Furthermore,　electron　paramagnetic　resonance　(EPR)　and　radical　trapping　experiments　indicate　that　1O2　and　SO4•-　involving　oxidation　mechanism　impart　maximum　contribution　towards　TBZ　degradation.　The　possible　pathways　of　TBZ　degradation　are　reasonably　proposed　by　the　HPLC-MS　and　the　toxicity　evolution　of　TBZ　is　appraised　using　the　ECOSAR　software.　This　study　provides　an　insight　into　the　fabrication　of　S-scheme　heterojunction　for　environment　remediation　through　the　photocatalysis/sulfate-mediated　advanced　oxidation　process.　©　2023