(Star polystyrene)-block-(linear polydimethylsiloxane)-block-(star polystyrene) triblock copolymers were synthesized by making living star-shaped polystyrenes through a convergent living anionic polymerization procedure, followed by ring-opening polymerization of hexamethylcyclotrisiloxane (D-3) then difunctional coupling. The molecular weights of the resulting polymers were characterized by gel permeation chromatography (GPC), multi angle laser light scattering (MALLS) and H-1 NMR spectroscopy. Triblock copolymers with relatively narrow molecular weight distributions were obtained.