Ta4+ doped Ta2O5 quantum dots were successfully prepared by vapor hydrolysis method with excellent visible light response. TaOC chemical bond highly enhanced the charge separation between Ta4+ doped Ta2O5 quantum dots and cotton-like g-C3N4. The Ta4+ doped Ta2O5/g-C3N4 showed superior photocatalytic performance for hydrogen production and RhB degradation. Direct Z-scheme photocatalytic mechanism of TCN catalyst was proposed.