A new ionic polyacetylene having perfluorinated benzyl substituent, poly(2-ethynyl-N-heptafluorobenzylpyridinium iodide), was synthesized via the direct polymerization of the quaterinazed acetylenic pyridinium monomers. The polymerization proceeded homogeneously without any additional initiator or catalyst to give a moderate yield of polymer. The results of instrumental analyses on the molecular structure of polymer revealed that the polymer have polyacetylene backbone system with N-heptafluorobenzylicpyridinium iodide as substituent. The photoluminescence (PL) spectra of polymer exhibited that the PL peak is located at 550 nm, corresponding to a photon energy of 2.26 eV. The irreversible electrochemical behaviors of polymer between the doped and undoped peaks were observed in the cyclic voltammograms of polymer. The initial oxidation and reduction of poly(EHFBPI) occurred at 0.53 V and -0.75 V (vs Ag/AgNO3). HOMO level of poly(EHFBPI) was 5.27 eV.