For the first time, the high-activity, single-site mesoporous WO3-MCF materials were synthesized and characterized by N2 sorption, TEM, UV-vis DRS, UV-Raman, and XPS. It was found that the dispersion and nature of the tungsten species depend strongly on the tungsten oxide content and the support characteristic. The novel catalyst remains a highly ordered mesostructure of the silica support. The catalytic performance of the materials in the epoxidation of cycloocta-1,5-diene with aqueous H2O2 was investigated. The excellent catalytic performance of WO3-MCF in the selective oxidation of cycloocta-1,5-diene was attributed to the presence of isolated tetrahedral {WO4} species and the unique pore structure. The novel catalyst can be easily recycled after reaction and reused many times with no significant loss of activity. The good stability can be attributed to the presence of isolated tungsten species anchored on thesupport through W-O-Si covalent bonds.