A new ionic polyacetylene derivative with benzodioxane moieties as a substituent was prepared via the in-situ quaternization polymerization of 2-ethynylpyridine using 2-bromomethyl-1,4-benzodioxane. The polymerization of monomeric ethynylpyridinium salts, which were formed by the firstly quaternization of 2-ethynylpyridine using 2-bromomethyl-1,4-benzodioxane, proceeded well to provide the corresponding polyacetylene derivative in 70% yield. The polymer structure was characterized by various instrumental methods to have the conjugated polymer backbone system with the benzodioxane pyridinium moieties. This ionic conjugated polymer was soluble in polar organic solvent such as methanol, DMF, DMSO, NMP, etc. This polymer had an ionic pyridinium moieties, it showed relatively more hygroscipic properties in air. The electro-optical and electrochemical properties of the resulting polymer were measured and discussed. The irreversible electrochemical behaviors were observed between the oxidation and reduction peaks. The present polymer exhibited stable redox behavior up to 50 cycles and a steady oxidation current at 1.0V, similar to other polyacetylene derivatives with pyridinium substituents.