The ordered mesoporous silica MCM-41 was covalently grafted with (3-chloropropyl)trimethoxysilane. Chloro substitution by the anion [4-CH₂-4′-Me-2,2′-bipyridine]⁻ gave a ligand-silica containing ca. 0.3 mmol bipyridyl groups per gram. Powder X-ray diffraction and nitrogen adsorption–desorption analysis demonstrated that the textural characteristics of the support were preserved during the grafting experiments and that the channels remained accessible, despite sequential reductions in surface area, pore volume and pore size. The coupling reactions were monitored by ²⁹Si MAS NMR and ¹³C CP MAS NMR spectroscopy. Bipyridyl-functionalized MCM-41 exhibits a high encapsulating ability, as evidenced by its interaction with a dichloromethane solution of MoO₂Cl₂(THF)₂. A material with a metal loading of 8.3 mass% was obtained. Molybdenum K-edge EXAFS analysis could not substantiate the formation of a tethered complex of the type MoO₂Cl₂(N–N), but instead indicated the formation of unidentate-bridged entities of the type [O₂Mo–X–MoO₂] with a metal–metal separation of 3.28 Å. The molybdenum-containing MCM was active as a catalyst for the epoxidation of cyclooctene by tert-butyl hydroperoxide. However, this activity is due, at least in part, to leached molybdenum species in solution.