The invention discloses a method for preparing a tri block copolymer of the formula: comprising: (a) contacting a cycloalkene with a chain transfer agent of the formula: Z—Y═Y—Z  in the presence of a metal carbene metathesis catalyst to form a telechelic polymer; and (d) contacting the telechelic polymer with an alkene of the formula  in the presence of an ATRP organometallic catalyst wherein n and m are integers; Z is an ATRP initiator and —Y═Y— is an alkenyl group; and, R′ is selected from the group consisting of aryl, nitrile and C1-C20 carboxylate, wherein R′ is substituted or unsubstituted. The invention also discloses a method for preparing a diblock copolymer. In addition, the invention encompasses a triblock copolymer having no 1,2-PBD structure in the PBD portion of the copolymer.