A series of Fe3+-doped TiO2 photocatalytic materials (Fe3+/TiO2) with a hollowfiber structure were successfully prepared using cotton fiber as the template. Thermo-gravimetric (TG), scanning electron microscopy (SEM), X-ray diffraction (XRD), zeta potential, infrared spectroscopy (IR), and UV-visible spectroscopy (UV-Vis) were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. Using the degradation of methylene blue (MB) as a model reaction, the photocatalytic properties of the samples with different amounts of Fe3+-doped were investigated. Results showed that a large number of nanosized particles existed on the surface of the fiber materials with hollow structures, indicating that these materials had a large specific surface area. Fe3+ ions were possibly well distributed in the lattice structure of anatase TiO2 and partially replaced Ti4+ which caused a broadening of the spectral response of TiO2 and also caused defects in the crystal structure. The fiber structure material showed better photocatalytic properties for the degradation of MB than pure TiO2 under solar light and the amount of Fe3+-doped significantly affected the catalytic property. On the surface of the fiber material with 0.15% (w) of Fe3+-doped, the decolorizing efficiency of the MB solution reached 93% at radiation time of 2 h and remained above 90% upon repetition (5 times). The material was easily removed by centrifugal separation. Therefore, using the template method and by doping with Fe3+, TiO2 may hopefully become a low-or non-energy consuming, high activity and green environmentally friendly catalytic material.