Abstract：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.