N, S, F—co-doped TiO2 visible-light response photocatalyst(N—S—F—TiO2) was prepared with TiCl4, thiourea and ionic liquid (［C6mim］+［BF4］-) via the microwave-catalytic hydrolysis precipitation process followed by calcination in an NH3/N2 atmosphere. It was characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and ultraviolet-visible diffusion reflectance spectroscopy(UV-Vis/DRS). Results showed that it was high purity anatase. The Ti—O—N, Ti—O—S and Ti—S bonds were formed in the TiO2 crystal and F used to dope TiO2 in the form of TiOF2. In the visible region 400~550 nm, it has strong absorption, and in 600~800 nm there was a strong absorption band. N—S—F—TiO2 prepared at volume ratio of ［C6mim］+［BF4］-/H2O of 5/95 exhibited the highest photocatalytic activity, and the degradation ratio of methyl orange was 95% under visible-light irradiation for 200 min. Multi-element co-doped synergistic effect was demonstrated by enhancement of the absorption in the visible region and higher visible light photocatalytic activity for N—S—F—TiO2.