High photoactive TiO2 catalyst was prepared using the sol-gel method through UV irradiation during the formation stage of nuclei. The surface morphology and microstructure of the prepared catalyst were characterized using scanning electron microscopy(SEM), X-ray diffraction patterns (XRD), and Fourier transform infrared spectroscopy (FT-IR). The photoactivity was evaluated by the degradation of methylene blue. The results show that the photocatalysis of the prepared catalyst is higher than that of conventional heat-treated particles. The higher photoactivity is a combined result of favorable microstructure, appropriate hydroxyl groups, and active sites of Ti3+ ions on the surface of TiO2. It is concluded that the ultraviolet irradiation-induced sol-gel method is an effective method to enhance the photocatalysis of TiO2.