The alpha-Fe2O3 fibers have been prepared by electrospinning the corresponding sol-gel precursor, then these fibers were characterized by TGA, SEM, XRD, BET and FT-IR respectively, indicating that the hierarchical alpha-Fe2O3 nanostructured fibers came into being. Photocatalytic degradation of methylene blue (MB) in water was carried out under ultraviolet (UV) light, showing that the fibers had better efficiency for removing MB than other catalysts. And several process parameters have also been studied, which showed that the removal effect of MB was influenced by the process parameters, such as the initial dye concentration, catalyst amounts, inorganic anions, and so on.