Heterostructured CeO₂/TiO₂ composite nanofibers were prepared via combination of hydrothermal growth and electrospinning technique. The morphology and structure of CeO₂/TiO₂ composite nanofibers were characterized by X-ray diffraction (XRD), Raman microscope (Raman), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and Brunauer-Emmett-Teller surface area (BET) analysis. The catalytic properties of the sample were studied via rhodamine B degradation as the model reaction. The results showed that CeO₂ nanoparticles could evenly grow on the TiO₂ nanofibers surface and thus heterostructured CeO₂/TiO₂ composite materials were successfully obtained. By selecting different alkaline source, CeO₂/TiO₂ heterostructures with different morphology of CeO₂ nanostructures were facilely fabricated. The CeO₂/TiO₂ heterostructures showed enhanced photocatalytic efficiency compared with the bare TiO₂ nanofibers under UV light irradiation. This is due to the reason that the presence of CeO₂ nanostructures on TiO₂ nanofibers can increase its surface area, and effectively achieve the separation of photoelectrons and holes, and thus enhancing the systems quantum efficiency. Last, the mechanism for the enhancement of photocatalytic activity of heterostructured nanofibers was discussed.