Heterostructured gamma-Bi2O3/TiO2 composite fibers were prepared via combination of solvothermal method and electrospinning technique. X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscope (EDS), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM) and UV-Vis absorption spectra were used to characterize heterostructured gamma-Bi2O3/TiO2 composite fibers. The photocatalytic properties of the heterostructured samples were evaluated by degrading rhodamine B (RB) under visible light irradiation. The results showed that gamma-Bi2O3 nanosheets could evenly grow on the TiO2 fibers surface and thus heterostructured gamma-Bi2O3/TiO2 composite fibers were successfully obtained. The absorption range of the as-obtained heterostructured samples were extended to the visible light region. Moreover, the presence of gamma-Bi2O3 nanostructures/TiO2 fibers heterostructures was beneficial to separation of photo-generated electrons and holes which enhanced the system's quantum efficiency. In comparison with that of pure TiO2 nanofibers, the gamma-Bi2O3/TiO2 heterostructures have enhanced photocatalytic efficiency under visible light irradiation, and the decolorizing efficiency of RB solution can reach 87.8%.