Photocatalytic TiO2 thin film is prepared by sol-gel technique on microstructured silicon substrate produced by femtosecond laser cumulative irradiation. The photocatalytic activity is evaluated by the degradation of methylene blue (MB) solution under ultraviolet (UV) irradiation. For 6-ml MB solution with initial concentration of 3.0 \times 10^{-5} mol/L, the degradation rate caused by TiO2 thin film of 2-cm2 area is higher than 70% after 10-h UV irradiation. Microstructured silicon substrate is found to enhance photocatalytic activity of the TiO2 thin film remarkably. The femtosecond laser microstructured silicon substrate is suitable to support TiO2 thin film photocatalysts.