The well-defined two-dimensional (2D) hexagonal mesoporous nanocrystalline anatase TiO2 was synthesized by the nonhydrolytic evaporation-induced co-assembly (EISA) of non-ionic amphiphilic triblock-copolymer template, titanium tetrachloride and tetrabutyl titanate. The ordered mesoporous TiO2 (M-TiO2) Was loaded with different % of Bi2O3 using the wet impregnation method. For comparison Degussa P25 impregnated with Bi2O3 was also prepared. The samples were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy, photoluminescence spectra (PLS), Fourier transform infrared spectra (FT-IR), N-2 adsorption-desorption (BET) and X-ray photoelectron spectroscopy (XPS) techniques. XRD and Raman spectra showed the pore wall was composed of anatase. 1.0% Bi2O3 loaded M-TiO2 revealed the well-ordered mesostructure. UV-vis diffuse reflectance spectroscopy measurements showed an extension of light absorption into the visible region. PLS analysis indicated that the electron-hole recombination rate have been effectively inhibited when Bi2O3 was loaded with ordered M-TiO2. The photo oxidation efficiency was evaluated by methyl orange (MO) and 2,4-dichlorophenol (2,4-DCP) degradation under visible illumination. The samples loaded with different % of Bi2O3 showed higher photocatalytic activity than M-TiO2 and Bi2O3 loaded P25. The catalyst exhibited high activity due to the Bi2O3-photosensitization and well-ordered 2D pore structure. The ordered mesoporous channels facilitate mass transport of the organic pollutants. TiO2 could extend the spectral response from UV to visible region because of Bi2O3-photosensitization which make the Bi2O3 loaded M-TiO2 photocatalyst visible light responsive. (C) 2009 Elsevier B.V. All rights reserved.