A new conjugated polyelectrolyte with the N-(3-butynyl)pyridinium bromide was synthesized via the non-catalyst polymerization of 2-ethynylpyridine by using 4-bromo-1-butyne. The polymerization proceeded well to give the resulting poly[N-(3-butynyl)-2-ethynylpyridium bromide] in 75% yield. The chemical structure of poly[N-(3-butynyl)-2-ethynylpyridium bromide] was characterized by such instrumental methods as IR, NMR, and UV-visible spectroscopies to have the conjugated backbone system with the designed substituents. The electro-optical and electrochemical properties of polymer were measured and discussed. Comparing absorption spectrum and cyclic voltammetry data, this polymer had the HOMO and LUMO values of 5.33 and 3.35?eV, which means the band gap of 1.98?eV.