Poly(2-ethynyl-N-hexylpyridinium iodide) was synthesized, by the direct polymerization of 2-ethynylpyridine and the corresponding 1-iodohexane, without any additional initiator or catalyst under mild reaction conditions in high yield (95%). Similar homologues possessing different counteranions were prepared by the ion-exchange reaction of the resulting poly(2-ethynyl-N-hexylpyridinium iodide). The polymer structures were found using various instrumental method to have conjugated polymer backbone systems of N-hexylpyridyl moieties and the corresponding counteranions. When comparing the maximum wavelengths in UV-vis and PL spectroscopic data, there is no particularly special effect that the counter anions have in these polymers. The photoluminescence peaks of these ionic conjugated polymers are located at 598~608 nm, which correspond to photon energies of 2.08~2.04 eV. The resulting thin films exhibited reversible electrochemical behavior between the doping and undoping peaks.