A novel synthetic route to new classes of polymeric coupling agents using substituted epoxy monomers is reported. In the presence of an initiating agent and tris(pentafluorophenyl)borane catalyst, substituted epoxy monomers bearing polyalkylene oxide and trialkoxysilane moieties undergo a ring-opening polymerization. The polymerization is highly versatile and allows for the fine-tuning of functional, structural, and architectural features of the resulting polymeric coupling agents. These new polyalkylene oxides substituted with organosilyl groups are capable of bonding to and modifying inorganic surfaces. The products of this invention form thin hydrophilic films.