In this work, we have used the bubble template solvothermal method to prepare TiO₂ Hollow Spheres (THS) for in situ growth of WS₂ on their surfaces and a three-phase TiO₂ Hollow Spheres/WS₂ (THS/WS₂) heterostructure composite. We also investigated the influence of W/Ti molar ratio on the morphology, structure, and optical properties of the delaminated THS/WS₂ composite and studied its photocatalytic activity to degrade RhB in visible light. Experiment result expresses that THS/WS₂-0.20 material shows the best photocatalytic activity, which is 3.9 times higher than that of THS alone. On this basis, the process of photogenerated charge carriers and photocatalytic charge transfer on the surface of the delaminated THS/WS₂ composite was elucidated, which provides a technical support for the fabrication and research of the mechanism of a three-dimensional TiO₂-based heterojunction photocatalyst.