One-dimensional mesoporous TiO2-Bi2WO6 hollow superstructures are prepared using a hydrothermal method and their photocatalysis and recycle properties are investigated. Experimental results indicate that anatase TiO2 nanoparticles are coupled with hierarchical Bi2WO6 hollow tubes on their surfaces. The TiO2-Bi2WO6 structure has a mesoporous wall and the pores in the wall are on average 21 nm. The hierarchical TiO2-Bi2WO6 heterostructures exhibit the highest photocatalytic activity in comparison with P25, pure Bi2WO6 hollow tube and mechanical mixture of Bi2WO6 tube and TiO2 nanoparticle in the degradation of rhodamine B (RhB) under simulated sunlight irradiation. The as-prepared TiO2-Bi2WO6 heterostructures can be easily recycled through sedimentation and they retains their high photocatalytic activity during the cycling use in the simulated sunlight-driving photodegradation process of RhB. The prepared mesoporous TiO2-Bi2WO6 with hollow superstructure is therefore a promising candidate material for water decontamination use.