Novel alternating copolymers composed of anthracene moiety and halostyrene unit were synthesized by ring-opening polymerization of cyclic monomers, 10-methylene-9,10-dihydroanthryl-9-spiro-p-chlorophenylcyclopropane and its bromo derivative. Reversible addition fragmentation chain transfer and conventional free radical polymerizations were employed for the purpose. In both cases, the ring-opening polymerization proceeded predominantly to afford alternating copolymer containing anthracene unit in the main chain. Incorporations of optoelectronic groups, involving diphenylamine, carbazole, and phenothiazine, on the halostyrene moieties of the alternating copolymers were conducted by palladium-catalyzed reactions. Novel nonconjugated copolymers having perfect alternating structures were obtained, in which the alternate arrangement of two distinct electronic functionalities is formed owing to the ring-opening polymerization system. Resulting anthracene-based alternating copolymers having two distinct electronic functionalities exhibited characteristic fluorescence resonance energy transfer, as confirmed by UV-vis and fluorescence spectra.