Heterogeneous photocatalytic materials, titania–phosphotungstic acid nanocomposites in the mesopores of SBA-15 (TiO2-H4PW12O40/SBA15) were prepared by sol–gel method. Compositions and structures of the nanocomposites were characterized by X-ray diffraction (XRD), UV-visible absorption spectroscopy and transmission electron microscopy (TEM). Uniform mesoporous SBA15 consisting of long-range channels provides the immobilization of titania-phosphotungstic acid nanocomposites. The photocatalytic activity of the prepared TiO2-H4PW12O40/SBA15 powders was evaluated from an analysis of the photocatalytic degradation of methyl orange. The results indicated that photocatalytic activity increased with the amount of H4PW12O40 from 0% to 10% and decreased when the amount of H4PW12O40 was above 10%. It is due to the synergetic reaction of H4PW12O40 and TiO2. However, much more H4PW12O40 can occupy the active center of TiO2. TiO2 can inhibit the decomposition of H4PW12O40 in the TiO2-H4PW12O40/SBA15 composites. On the other hand, H4PW12O40 repressed the TiO2 particle growth during calcination process. The composite catalyst also had the advantage of easily being recovered and reused.