The successful adjustment of phase composition and morphology of hierarchical TiO2 nanobelts, which feature homoepitaxial nanobranches, has been developed via the hydrothermal method and chemical bath deposition technique. Effects of hydrothermal reaction time, titanium butoxide treatment in chemical bath deposition, and calcination temperature are systematically investigated. For the first time, three-step ultrafast electron transfers between the band edges of the engaged phases are realized through the enhanced photocatalytic activity results. Growth mechanism related to branch density control on nanobelt surface under such soft chemical process is discussed in detail on the basis of classical nucleation theory. The current work might provide new insights into the fabrication of one-dimensional homoepitaxial branched TiO2 nanostructures as high performance photocatalysts and facilitate their application in environmental cleanup.