Improving　the　spatial　separation　of　photogenerated　charge　carriers　and　enhancing　the　direct　electron　utilization　are　crucial　for　photocatalytic　materials　and　their　application　in　water　purification.　In　this　study,　a　novel　heterojunction,　CoFe　layered　double　oxides　encapsulated　by　oxygen-vacancy-rich　BiOBr　(CoFe-LDO/BiOBr-OV,　shortened　to　CFB),　was　successfully　synthesized　for　the　removal　of　halogenated　disinfection　by-products　bromate　and　trichloroacetamide　(TCAcAm)　under　simulated　solar　light.　Advanced　characterization　techniques　and　density　functional　theory　calculations　demonstrated　that　the　enhanced　photoelectrochemical　properties　of　CFB　can　be　attributed　to　the　heterojunction　effect　and　OVs　incorporation.　The　internal　electric　field　between　CoFe-LDO　and　BiOBr-OV　facilitated　S-scheme　charge　transfer,　and　more　available　electrons　were　retained　a　relatively　negative　redox　potential　position　onto　the　heterojunctions.　Meanwhile,　the　OVs　in　BiOBr　further　alleviated　the　consumption　of　electrons　caused　by　dissolved　oxygen　to　some　extent.　Owing　to　the　efficient　dehalogenation　mediated　by　electron　transfer,　the　photocatalytic　process　of　CFB　achieved　the　complete　removal　of　bromate　and　TCAcAm　after　20　min　and　3　h,　respectively.　The　dehalogenative　removal　rate　of　CFB　approached　430,　39　and　5.7-fold　higher　than　those　of　CoFe-LDO,　BiOBr　and　BiOBr-OV,　respectively.　Additionally,　the　ecotoxicity　evaluation　based　on　the　behavior　of　zebrafish　larvae　indicated　that　the　dehalogenative　removal　process　of　bromate　and　TCAcAm　resulted　in　favorable　detoxification.　This　work　provides　valuable　guidance　for　the　design　and　application　of　S-scheme　heterojunction　photocatalysts　in　the　advanced　treatment　of　halogenated　micropollutants.　©　2025　Elsevier　B.V.