PVP/Ti(OC4H9)(4)/N5H37W6O24 center dot H2O precursors with different Ti/W molar ratios were successfully synthesized by a simple combination method of Sol-Gel and electrospinning techniques. The electrospun precursors was converted into TiO2/WO3 micro-nanofibers via calcination at different temperatures in air. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (FE-SEM) and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis) techniques. Photocatalytic activity was evaluated by degradation of methylene blue (MB) under ultraviolet light irradiation. The results showed that WO3-doped TiO2 micro-nanofibers with Ti/W molar ratio of 12:1 and TiO2/WO3 micro- nanofibers with Ti/W molar ratio of 4:1 after calcination at 500 degrees C exhibited better photocatalytic degradation activity than that of pure TiO2 micro-nanofibers.