Atom transfer radical polymerization was used to prepare well-defined vinyl polyoxadiazole homomacromonomers with a properly modified a-dicarboxylic acid methyl ester as the initiator. Macromonomers of various molecular weights with narrow polydispersities in some cases were obtained, as proved by gel permeation chromatography (GPC). The structures of the obtained macromonomers were then identified with H-1 NMR spectroscopy. These macromonomers were subsequently copolymerized with a dihydroxy anthracene based monomer by a polycondensation technique, and this resulted in polymacromonomers. Coil-rod-coil copolymers containing side-chain anthracene and oxadiazole units were also synthesized by atom transfer radical polymerization. The resulting copolymers combined an anthracene derivative as the rigid block with a random copolymer of the desired anthracene- and/or oxadiazolebased monomers as the flexible block. These copolymers were primarily characterized with GPC and H-1 NMR techniques. Additionally, the optical properties of all these copolymers were investigated in detail, and they suggested energy transfer from the oxadiazole to the anthracene chromophores, which became much more efficient in the solid state. (C) 2005 Wiley Periodicals, Inc.