In this study, we synthesized a series of dendritic polystyrene-b-linear poly(t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene(Mn＝1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly(t-butyl acrylate)s were prepared by an atom transfer radical polymerization(ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly(t-butyl acrylate)s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under H2 atmosphere. In the final step, dendriticlinear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino)pyridine(DMAP) and N,N′-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by 1H-NMR spectroscopy and gel permeation chromatography(GPC).