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.