Titanium dioxide nanoparticles (TiO(2)NPs) embedded carbon nanofibers (CNFs) have been successfully prepared by electrospinning technique, solvothermal synthesis and high-temperature calcination processes. The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-Vis diffuse reflectance spectra (DRS) and Fourier transform infrared (FTIR) spectra. The results of characterization revealed that solvothermal treatment and high-temperature calcination were beneficial to the synthesis of anatase TiO2. Compared to the as-fabricated TiO2 powder, TiO2 NPs contained in the TiO2/CNFs were successfully grown on the surface of CNFs without aggregation. The photocatalytic activities of the TiO2/CNFs heterostructures were evaluated by the degradation of methyl orange (MO) under UV light irradiation for 14 h. The TiO2/CNFs exhibited higher photocatalytic activities than pure TiO2 powder, which were attributed to the small size of TiO2 NPs, electron transfer, high adsorption properties of CNFs and the formation of heterostructures between TiO2 and CNFs. Moreover, in aqueous solution, the as-prepared TiO2/CNFs could be easily recycled for the application of CNFs.