Oxygen-deficient　TiO　2　/WO　3　constructed　via　the　controllable　temperature　of　hydrogen　annealing　is　designed　in　view　of　combining　the　broad　visible　spectrum　absorption　with　the　prominent　coupled　semiconductor　properties.　Surface　lattice　disorder　of　TiO　2　/WO　3　arises　at　hydrogen　annealing　temperature　of　200　and　300　°C,　while　critical　phase　transition　from　TiO　2　/WO　3　to　TiO　2　/WO　2.9　occurs　at　400　°C,　both　of　which　can　introduce　oxygen　vacancies.　The　hydrogenated　TiO　2　/WO　3　with　rich　surface-oxygen-vacancies　exhibits　much　higher　photocatalytic　activity　for　decomposition　of　gaseous　toluene　than　pristine　TiO　2　/WO　3　under　visible-light　illumination　(λ>　420　nm).　The　photoelectrochemical　analysis　shows　that　the　improved　electronic　properties　of　oxygen-deficient　TiO　2　/WO　3　enable　dramatically　efficient　promotion　of　photoinduced　charge　transfer　and　separation,　which　is　the　key　factor　for　the　improved　photocatalytic　activity.　It　is　hoped　that　the　present　work　could　boost　ongoing　interest　for　preparing　various　hydrogenated　coupled　semiconductors　with　enhanced　activity　for　diverse　photocatalytic　applications.　©　2017　Elsevier　B.V.