In this work, the enhanced charge transfer in CaTiO₃/Pr³⁺-Y₂SiO₅/RGO catalyst was achieved by assembled RGO with CaTiO₃ and Pr³⁺-Y₂SiO₅ in visible light driven water splitting. By taking advantage of upconversion luminescence material Pr³⁺-Y₂SiO₅ (Pr³⁺-YSO), visible light was upconverted into UV light and was used to excite UV responded nano-CaTiO₃ to form charge pairs. Then the efficient forward charge transfer to hydrogen generation site Pt was fulfilled over RGO. Longer life time of charges was confirmed by fluorescence spectra in this catalyst. Simultaneously, removing nascent formed oxygen from reaction mixture by an artificial gill significantly inhibited hydrogen–oxygen reverse recombination reaction. By those technologies application, visible-light-driven overall water splitting was accomplished. The photocatalytic activity for hydrogen generation has been raised up to 480% with excellent stability in three recycle reactions. This photocatalyst system is efficient for visible overall split water over UV-responsive photocatalysts.