Tungsten　oxide　(WO3)　and　copper　oxide　(CuO)/WO3　samples　were　prepared,　and　their　photocatalytic　performance　towards　the　reforming　of　CH3OH　to　hydrogen　was　compared　under　visible　light　irradiation　at　ambient　temperature.　CuO/WO3　had　an　approximately　64　times　higher　hydrogen　production　activity　than　bare　WO3.　CH3OH　accepted　electrons　from　WO3　but　provided　electrons　to　CuO/WO3　thin　films,　indicating　that　the　hydrogen　production　from　CH3OH　was　related　to　electron　transfer　during　CH3OH　adsorption.　The　characterization　results　showed　that　Cu　exists　in　a　mixed-valence　state　in　CuO/WO3,　which　activated　the　lattice　oxygen　of　WO3　to　form　the　corresponding　interfacial　oxygen　vacancies　(VOs).　The　oxygen　atom　of　CH3OH　was　fixed　at　VOs　sites,　which　facilitated　the　cleavage　of　the　O[sbnd]H　bond.　Cu2+　sites　favored　the　cleavage　of　the　C[sbnd]H　bond　in　CH3OH　because　VOs　fixed　the　oxygen　atom.　Then,　the　production　of　hydrogen　via　these　two　processes　was　accompanied　by　the　transfer　of　electrons　from　CH3OH　to　Cu2+　sites　at　the　interface.　This　was　followed　by　hydrogen　production　after　accepting　photogenerated　electrons　from　WO3.　The　reason　for　the　low　catalytic　activity　of　the　WO3　support　was　that　it　contained　no　VOs　nor　Cu2+　sites　to　oxidize　CH3OH　to　produce　more　protons.　This　study　provides　an　approach　to　improve　catalysts　used　for　the　photocatalytic　reformation　of　methanol.　©　2023　Elsevier　B.V.