TiO2 sol was prepared for the degradation of methylene blue (MB) solution under ultraviolet (UV) irradiation. The absorption spectra of MB indicated that the maximum wavelength, 663 nm, almost kept the same. The performance of 92.3% for color removal was reached after 160 min. The particle size of TiO2 sol was about 22.5 nm. X-ray diffraction showed that TiO2 consisted of a single anatase phase. The small size and anatase phase probably resulted in high photocatalytic activity of TiO2 sol. The degradation ratio decreased as the initial concentration of MB increased. The photodegradation efficiency decreased in the order of pH 2>pH 9>pH 7. Regarding catalyst load, the degradation increased with the mass of catalyst up to an amount of 1.5 g⋅L−1 then decreased as the mass continued to increase. The addition of H2O2 to TiO2 sol resulted in an increase on the degradation ratio.