The straightforward synthesis of a polystyrene-arm polybutadiene-arm-poly(methyl methacrylate) triarm star copolymer has been successfully realized by a sequence of reactions which involves the sequential addition of a living polybutadienyllithium to a polystyrene macromonomer with a terminal 1,1-diphenylethylene unit and subsequent polymerization of methyl methacrylate. The high-molecular-weight polystyrene-arm-polybutadiene-arm-poly(methyl methacrylate) star copolymer shows microphase separation into three phases.