Mesoporous TiO2 samples with high crystallinity have been successfully synthesized by a fast sol-gel method using polyethylene glycol (PEG) and polyacrylamide (PAM) as composite templates using two-step calcining processes. The samples have been characterized by X-ray diffraction, Transmission electron microscopy, N-2 adsorption-desorption and Diffuse reflectance UV-visible absorption spectra. The results show that the sample exhibits typical mesoporous structure and high crystallinity. The effects of PEG on properties of the samples and the effect of PAM on sol-gel reaction rate have also been studied. The results show that, PAM accelerates gel rate and PEG increased the crystallinity and specific surface area of the sample. Besides, visible light photocatalytic activity of mesoporous TiO2 prepared by the fast sol-gel method is found to be improved.