A gold doped titanium dioxide (TiO2) nanofiber was prepared by one-step electrospinning technique to control the DC high voltage and the following calcination. The crystal structures and morphology of Au-TiO2 nanofibers were characterized in detail by X-ray diffraction (XRD), energy dispersive photoelectron spectroscopy (EDS), scanning electron microscope (SEM) and transmission electron microscope (TEM). These results indicate that Au is successfully incorporated into TiO2 nanofibers without gold loss, while Au and TiO2 form a heterogeneous structure. It implied that the Schottky barrier existed by X-ray photoelectron spectroscopy (XPS) of 0.075% Au-TiO2. For 0.075% Au-TiO2 nanofibers, the rate of photocatalytic degradation of methylene (MB) was significantly higher than that of pure TiO2 nanofibers.