Hierarchical TiO₂-Bi₂MoO6 nanospheres as efficient visible-light responsive photocatalyst are fabricated by dispersing brookite TiO₂ nanorods on the hierarchical Bi₂MoO6 nanospheres, which provides visible-light absorption and large surface area. The morphologies, surface area and light absorption features of as-prepared TiO²-Bi²MoO6 can be rational controlled by varying the loading amount of TiO² nanorods on hierarchical Bi²MoO6 nanospheres. As a result, the TiO²-Bi²MoO6-3 yields 380 ppm CO² production for decomposing 2-propanol at 11 h under visible light irradiation, realizing 4.4 times enhancement of photocatalytic property with respect to pure TiO² nanorods. Moreover, the three-dimensional hierarchical architecture enables the hybrid TiO²-Bi²MoO6 excellent cycling stability.