Porous TiO2 films were prepared through dip-coating on glass substrates using composite templates of PEG and ODA. Photocatalytic activity of the photocatalyst was evaluated by measuring removal rate of aqueous methyl orange under UV light irradiation. The addition of composite templates had obvious influence on surface morphology of the films. Layered and porous structures formed in the surface due to the function of templates. When the amount of PEG in the composite template increased from 0.1 g to 1.9 g, adsorption edge of the films moved to longer wavelength region. When the amount of PEG increased to 1.0 g, there were sharp decrease of specific surface area and cumulative pore volume. The improving photocatalytic activity as a result of addition of PEG can be noticed.