In order to intrinsically boost the photocatalytic performance of WO3/CdS, the charge transfer route can be modulated from conventional type-II to Z-scheme by incorporating of hydrogen ions into WO3/CdS to form H0.53WO3/CdS. This work indicates that only when charge transfer of WO3/CdS is type-II, can H0.53WO3/CdS composite be formed in-situ. Subsequently, the Z-scheme photocatalytic mechanism plays its prominent roles in gradually improving photocatalytic H-2 evolution performance. H0.53WO3/CdS has high photocatalytic activity for hydrogen production, which is much higher than that of WO3/CdS. This work will provides an in-depth understanding of charge separation and transfer processes and steer charge flow in a Z-scheme manner for efficient solar-to-chemical energy applications.