A　novel　method　for　the　synthesis　of　bismuth　(Bi)　nanospheres　on　the　surface　of　BiOBr/TiO2　nanocomposites　is　presented,　which　can　be　used　for　controllable　preparation　of　BiOBr/TiO2　and　Bi/BiOBr/TiO2　heterojunction　films.　The　synthesis　temperature　of　the　one-pot　glycol-assisted　solvothermal　method　is　the　key　factor　affecting　the　formation　of　Bi　nanospheres　and　the　loading　of　BiOBr　nanosheets.　The　structural　and　optical　properties　of　the　films　were　characterized,　and　the　photocathodic　protection　property　of　the　prepared　photoanodes　under　different　solvothermal　temperatures　was　systematically　investigated.　The　reason　for　enhancing　the　photocathodic　protection　performance　of　Bi/BiOBr/TiO2　photoanode　by　introducing　Bi　nanospheres　was　also　explained,　and　it　was　found　that　the　photoanode　prepared　at　160　°C　has　the　best　performance.　Under　visible　light　illumination,　the　Bi/BiOBr/TiO2　photoanode　can　negatively　shift　the　potential　of　coupled　316　L　stainless　steel　to　430　mV　(vs.　SCE).　The　durability　tests　demonstrated　the　excellent　photochemical　stability　and　good　scouring　resistance　of　the　Bi/BiOBr/TiO2　photoanode.　Moreover,　a　charge　transfer　mechanism　for　Z-scheme　heterojunctions　was　proposed　based　on　the　electron　spin　resonance　characterization　results　of　the　Bi/BiOBr/TiO2　photoanode.　The　formation　of　Z-scheme　heterojunctions　is　mainly　attributed　to　that　the　Bi　nanospheres　play　a　＇bridge＇　role　between　BiOBr　and　TiO2,　which　realizes　the　Z-scheme　electron　transport　mechanism　in　the　Bi/BiOBr/TiO2　films.　©　2023　Elsevier　B.V.