The catalyst-free polymerization of quaternized pyridylacetylenes using appropriate reactants have been known a versatile synthetic platform for the ionically functionalized polyacetylenes. Here, we synthesized a polyelectrolytic polyacetylene derivative with naphthyl substituents in high yield via the catalyst-free quternization polymerization of 2-ethynylpyridine using 2-(bromomethyl)naphthalene. The monomeric 2-ethynylpyridinium salts formed in first reaction step was spontaneously polymerized to give the corresponding polyacetylene. The photoluminescence peak was observed at 509 nm corresponding to a photon energy of 2.44 eV. The cyclovoltamograms of polymer exhibited the electrochemically stable window at the –1.85 - 1.55 V region and two irreversible redox peaks at each oxidation and reduction voltage.