The present invention provides a hollow TiO2/MoS2 composite material, which has a hollow structure, wherein a MoS2 layered material forms a shell layer on the outer layer of the hollow TiO2/MoS2 composite material, and TiO2 is attached inside the shell layer, such that the visible light utilization rate can be increased with the structure so as to improve the photocatalytic efficiency. The invention further provides the preparation method of the hollow TiO2/MoS2 composite material, wherein the macromolecule polymer containing hydroxyl, amino or carboxyl is adsorbed on the TiO2 surface to provide the etching protection effect, and the fluoride etches the internal TiO2 so as to form the TiO2/MoS2 hollow structure.