In this paper, a facile two-step synthesis route combining an electrospinning technique and solvothermal method has been presented as a straightforward protocol for the exploitation of Bi2MoO6-carbon nanofiber (CNF) hierarchical heterostructures, which are composed of Bi2MoO6 nanosheets on the surface of CNFs. Photocatalytic tests show that the Bi2MoO6-CNF heterostructures possess a much higher degradation rate of Rhodamine B (RB) than pure Bi2MoO6 under visible light. The enhanced photocatalytic activity may be attributed to the extended absorption in the visible light region due to the Bi2MoO6 nanosheets, and the effective separation of the photogenerated carriers driven by the photoinduced potential difference produced at the Bi2MoO6-CNF heterojunction interface. Moreover, the heterostructures could be recovered easily by sedimentation without a decrease in their photocatalytic activity. The morphology of the secondary Bi2MoO6 nanostructures could be controlled by adjusting the experimental parameters, including the precursor concentration, temperature and solvent during the solvothermal process. As a result, different morphologies of Bi2MoO6-CNF heterostructures, with Bi2MoO6 nanosheets, nanoparticles, nanoflowers and nanorods, were successfully achieved.