Bi2WO6 nanofibers were synthesized by an electrospinning process. The phase, microstructure and photocatalytic performance of the obtained Bi2WO6 photocatalysts were investigated. The XRD patterns and FTIR spectrum suggest that Bi2WO6 nanofibers have the orthorhombic phase. The SEM and TEM images show that Bi2WO6 nanofibers have a rough surface and a large number of hollow caves. The Bi2WO6 hierarchical nanofibers show a high decomposition efficiency of MO under light irradiation. The higher photocatalytic activity of Bi2WO6 nanofibers results from the large specific surface area. The large specific surface area provides more surface active sits and makes an easier charge carrier transport.