A series of Mn-TiO(2)/SiO(2) (silica gel loaded with manganese doped TiO(2)) photocatalysts have been prepared by sol-gel method, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activities were enhanced in photocatalytic degradation of methyl orange over Mn-TiO(2)/SiO(2). XPS analysis shows that a Ti-O-Si or Ti-O-Mn bond is formed on the surface of photocatalyst. Mn is doped as a mixture of Mn(2+) and Mn(3+) on the surface of 1.0mol% Mn-TiO(2)/SiO(2). Mn(3+) appears to trap electrons and prohibit the electron-hole recombination. The electrons trapped in Mn(3+) site are subsequently transferred to the adsorbed O(2). As a result, the combination of the electron-hole pair was reduced.