N-doped mesoporous titania was synthesized using polyethylene glycol (PEG) as template and Dimethyl Formamide (DMF) as nitrogen source. The physical and photophysical properties of the photocatalyst were characterized by X-ray diffraction (XRD), FTIR, BET, transmission electron microscope (TEM), UV-Vis diffuse reflectance spectra (DRS), and X-ray photoelectron spectra (XPS). PEG played an important role in the preparation process within mesoporous titania. The N-doped mesoporous titania possessed diameter of ca. 20 nm with anatase crystalline structure, and had absorption in the visible region. N-doped mesoporous titania samples showed excellent photocatalytic activity for methyl orange (MO) degradation under visible light irradiation, which could be attributed to synergistic effect between the retained alkoxyls and the nitrogen doping.