Sulfur-doped TiO2 catalysts were prepared by a mechanochemical method. The prepared catalysts exhibited photocatalytic activity in methylene blue degradation under visible light. The catalyst structure has been characterized using UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry analysis (TGA) as well as Fourier transform infrared spectroscopy (FT-IR). UV-visible spectroscopy revealed that the absorption edge of the doped TiO2 was red-shifted compared with bare TiO2. XRD patterns suggested that the brookite phase became more prevalent with increasing ball milling duration. In addition, surface sulfate species were detected by FT-IR, XPS and TGA. We deduce the rise of catalytic activity is due to the synergetic effect between the brookite phase and the anatase phase that would probably retard the electron-hole recombination. On the other hand, methylene blue was found to be N-demethylated during the irradiation thus giving rise to blue-shifting of peak at 664 nm in UV-visible spectroscopy.