Precise graft copolymer architectures were achieved by combining the macromonomer technique with the acyclic diene metathesis (ADMET) reaction. These well-defined copolymer structures were the result of proper monomer design before metathesis polymerization. Features such as length of the graft, nature, and concentration of the graft site along the backbone were manipulated via the combination of living atom transfer radical polymerization methods with ADMET chemistry. Furthermore, the physical behavior of these materials was altered such that they presented dissimilar thermal properties of either the homopolymers or random copolymers. (C) 2003 Wiley Periodicals, Inc.