Chain-end- and in-chain-functionalized poly(phenyl vinyl sulfoxide) with a definite number of dimethylamino groups have been synthesized by living anionic polymerization of phenyl vinyl sulfoxide with functionalized initiators prepared from either 1-(4-dimethylaminophenyl)-1-phenylethylene or 1,1-bis(4-dimethylaminophenyl)ethylene with carbanionic species such as sec-BuLi, cumylpotassium and potassium naphthalenide. By the stoichiometric reaction of the dimethylamine-chain-functionalized poly(phenyl vinyl sulfoxide) thus prepared with ω-carboxylated poly-styrene and subsequent thermal treatment of the reaction mixture, novel block co-polymer and asymmetric star-branched polymers consisting of conducting polyacetylene (PA) and polystyrene segments via ionic interaction to form ionic bonds have been synthesized. The lamellar morphologies with conducting PA layers were observed in the cast films of such block co-polymer and star-branched polymer.