A new ionic polyacetylene with coumarin moieties was synthesized via the non-catalyst polymerization of 2-ethynylpyridine using 4-bromomethyl-7-methoxycoumarin in high yield. The polymerization proceeded well in homogeneous manner to give 75% of yield without any additional catalyst or initiator. The polymer structure was identified by such various instrumental methods as NMR, IR, and UV-visible spectroscopies to have a conjugated backbone with the designed coumarin groups. The photoluminescence peak was observed at 512nm corresponding to a photon energy of 2.42eV. The cyclovoltamograms of polymer exhibited the electrochemically stable window at the -1.8 approximate to 1.50V region. Oxidation and reduction were started at 0.58 and -0.8V and had stable electrochemical property up to 30 cycles.