Photocatalysis has attracted tremendous attention due to its great potential in environmental remediation, greener energy production and chemical synthesis. Developing highly efficient and easily recyclable photocatalysts is highly desirable for the practical applications. Herein, a novel macro-sized hierarchical porous titanosilicate (MHPTS) was prepared by the multi-template method to control the macroscopic shape and multiple levels of pore structures. MHPTS has uniform pass-through macropores, large pore volume, high specific surface area and mechanical strength, and the macropore wall is a continuous micro-mesoporous nanofilm. The in situ growth of nanocrystal TiO2 on the pore wall of MHPTS forms the macro-sized hierarchical nanostructured composite TiO2/MHPTS, which integrates the advantages of macro-sized macroporous materials and micro-mesoporous nanomaterials. MHPTS exhibits high photocatalytic degradation performance towards Rhodamine B (RhB) owing to its unique structure. On this basis, the incorporation of nano TiO2 into MHPTS remarkably improves the photocatalytic activity. This great improvement can be attributed to the highly dispersed TiO2 nanoparticles and the synergistic effect of MHPTS and TiO2 nanoparticles. The formation of Ti–O-Si bonds at the interface leads to the enhanced adsorption capacity for RhB and light absorption ability. The possible photodegradation mechanism is proposed according to the results of trapping experiments and photoelectrochemical tests. [ABSTRACT FROM AUTHOR]