A complex moiety containing VO(IV) was anchored covalently into organic-modified Si-MCM-41 to prepare a new catalyst. The prepared materials were characterized using various techniques. Several types of aromatic and aliphatic sulfides were successfully oxidized to the corresponding sulfoxides in good to excellent yields using H2O2 in the presence of a catalytic amount of the catalyst under solvent-free conditions. The results showed that the OH groups of the various compounds such as 2,2-(phenylthio)ethanol and 2-(methylthio)ethanol remained intact under similar conditions. Meanwhile the catalyst was stable in the reaction system, and could be reused at least four times without significant loss of its activity and chemoselectivity.