Z-scheme　photocatalysts　commonly　possess　both　high　charge　separation　efficiency　and　strong　redox　ability.　In　this　paper,　novel　3-dimensional/2-dimensional　(3D/2D)　structured　bismuth-rich　bismuth　oxide　iodide/bismuth　oxide　bromide　(Bi4O5I2/BiOBr)　hybrids　with　Z-scheme　heterojunctions　were　first　prepared.　The　in　situ　generated　I-3(-)/I-　and　Bi5+/Bi3+　redox　mediators　in　Bi4O5I2/BiOBr　hybrids　greatly　improve　their　photocatalytic　activity　toward　phenolic　contaminants.　Their　structure,　morphology,　optical　properties,　and　electrochemical　properties　were　characterized.　Scanning　electron　microscopy　images　demonstrated　that　the　2D　BiOBr　nanoplates　were　evenly　and　tightly　anchored　on　the　surface　of　the　3D　Bi4O5I2　microspheres.　This　novel　3D/2D　spatial　structure　was　beneficial　for　the　formation　of　heterojunctions　between　BiOBr　and　Bi4O5I2,　which　improved　the　quantum　efficiency　through　interfacial　charge　transfer.　The　Bi4O5I2/BiOBr　hybrids　exhibited　excellent　photocatalytic　activities　toward　o-phenylphenol　(OPP),　p-tert-butylphenol,　4-chlorophenol,　and　p-nitrophenol.　Bi4O5I2/BiOBr-5　possessed　the　best　activity　in　decomposing　OPP,　which　was　approximately　3.43　times　higher　than　that　of　pure　Bi4O5I2.　The　well-matched　energy　bands　of　components　in　the　hybrids　facilitated　the　interfacial　charge　separation　through　an　effective　Z-scheme　transfer　direction　guided　by　I-3(-)/I-　and　Bi5+/Bi3+　redox　mediators.　Based　on　the　results　of　electron　spin　paramagnetic　resonance　and　trapping　experiments,　a　mechanism　was　proposed　for　the　degradation　of　pollutants　using　the　Bi4O5I2/BiOBr　hybrids.　(C)　2022　Elsevier　Inc.　All　rights　reserved.