One-dimensional Bi₂MoO₆/TiO₂ hierarchical heterostructures with different secondary Bi₂MoO₆ nanostructures grown on primary TiO₂ nanofibers have been obtained by a combination of electrospinning and a solvothermal technique. The morphology of the secondary Bi₂MoO₆ nanostructures could be controlled by adjusting the precursor concentration, and then two different morphologies of Bi₂MoO₆/TiO₂ heterostructures with Bi₂MoO₆ nanoparticles and nanosheets were successfully achieved. Photocatalytic tests displayed that the Bi₂MoO₆/TiO₂ heterostructures possessed a much higher degradation rate of Rhodamine B (RB) than the unmodified TiO₂ nanofibers and Bi₂MoO₆ under UV and visible light. The enhanced photocatalytic activity could be attributed to the extended absorption in the visible light region resulting from the Bi₂MoO₆ nanosheets, and the effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the Bi₂MoO₆/TiO₂ heterojunction interface. Moreover, the heterostructures could be reclaimed easily by sedimentation without a decrease of the photocatalytic activity.