Fe-doped TiO2 nanoparticles were successfully synthesized by a hydrothermal method. The nanofibers consisting of Fe-doped TiO2, chitosan, and poly(vinyl alcohol) (PVA) were successfully prepared using an electrospinning method. Analytical methods including SEM, EDS, TEM, XRD, IR, and TGA were used to characterize the properties of the materials. Fe-doped TiO2 nanoparticles with an average diameter of 20 nm are well dispersed in the nanofibers with an average diameter of 177 nm. The materials were applied for methylene blue (MB) removal by using the combined methods of adsorption and photocatalysis. The total efficiency of MB removal is 94 wt% when the content of Fe-doped TiO2 nanoparticles in nanofibers is 20 wt%. The recovery and reuse of the nanofibers have also been performed with ease and efficiency, indicating that Fe-doped TiO2/chitosan/PVA nanofibers would be potential materials for adsorbents and photocatalysts.