Vinylbenzyl-terminated polystyrene (PS) and polyisoprene (PI) macromonomers were synthesized by the coupling reaction of corresponding living anions with p-chloromethylstyrene. Anionic copolymerizations of binary PS and PI macromonomers were carried out in benzene with n-butyllithium as an initiator. The reactivity ratios of these systems were close to an azeotropic copolymerization. We studied the microphase separation of A(n)B(n) star-like (comb-shaped) copolymers by electron microscopy. A(n)B(n) star copolymers formed clear microphase-separated structures and their domain sizes were smaller than those of corresponding diblock copolymers.