MoS2 nanosheet-coated TiO2 nanobelt heterostructures—referred to as TiO2@MoS2—with a 3D hierarchical configuration are prepared via a hydrothermal reaction. The TiO2 nanobelts used as a synthetic template inhibit the growth of MoS2 crystals along the c-axis, resulting in a few-layer MoS2 nanosheet coating on the TiO2 nanobelts. The as-prepared TiO2@MoS2 heterostructure shows a high photocatalytic hydrogen production even without the Pt co-catalyst. Importantly, the TiO2@MoS2 heterostructure with 50 wt% of MoS2 exhibits the highest hydrogen production rate of 1.6 mmol h−1g−1. Moreover, such a heterostructure possesses a strong adsorption ability towards organic dyes and shows high performance in photocatalytic degradation of the dye molecules.