TiO2-SiO2 (TiO2 supported on SiO2) photocatalysts were prepared using an ultrasonic-assisted sol-gel method. These photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence spectra (PL). Their photocatalytic activities were investigated by the method of methyl orange oxidation. It was found that the photocatalytic activity of TiO2-SiO2 was optimal when the molar ratio of hexadecyl trimethyl ammonium bromide to titanium butoxide was 1:10. The average crystallite size of TiO2-SiO2 was smaller than that prepared by the stirring method. Furthermore, for pure anatase phase samples, it was shown that the lower the photoluminescence intensity, the higher the photocatalytic activity.