In the present study, we synthesized a new conjugated polyelectrolyte with the N-(alpha-isobutyryl)pyridinium bromide as substituents via the spontaneous, catalyst-free polymerization of 2-ethynylpyridine using alpha-bromoisobutyryl bromide. The polymerization proceeded well to give the resulting poly[2-ethynyl-N-(alpha-isobutyryl)pyridium bromide] in high yield. The polymer structure was characterized by means of such instrumental methods as IR, NMR, and UV-visible spectroscopies to have the conjugated backbone system with the N-(alpha-isobutyryl)pyridinium bromides. Absorption spectrum of polymer showed the maximum peaks of 334 and 411 nm. The electrochemical property of polymer was measured and discussed. Based on cyclic voltammetry data, this polymer had the HOMO value of 5.25 eV.