Benzyl 6-(2'-pentamethyldisiloxanyl ethyl)-ortho-tolyl ketone (I) was prepared by a ruthenium-catalyzed Mural reaction of benzyl ortho-tolyl ketone with vinyl pentamethyldisiloxane. The reaction of I with a mixture of styrene and a catalytic amount of picoline Cu(II) acetate yielded the telechelic polystyrene alpha,omega-bis(2-pentamethyl-disiloxanyl ethyl)polystyrene (III). The acid-catalyzed equilibration polymerization of octamethylcyclotetrasiloxane into the Si-O-Si bonds of telechelic III yielded the polydimethylsiloxane-polystyrene-polydimethylsiloxane triblock soft-hard-soft copolymer. The molecular weights of the copolymers were studied by H-1 NMR end-group analysis and gel permeation chromatography. The thermal properties and morphology of TV were examined by differential scanning calorimetry and transmission electron microscopy (TEM).