Two poly(pyridinium salt)s with bulky organic counterions (tosylate and triflimide) were synthesized by either the ring-transmutation polymerization reaction of 4,4'-(1,4-phenylene)bis(2,6-diphenylpyrylium tosylate) with 1,12-diaminododecane on heating in dimethyl sulfoxide (DMSO) at 145150 C for 24 h or the metathesis reaction of the corresponding tosylate polymer with lithium triflimide in a common organic solvent such as acetonitrile. Their polyelectrolyte behavior in DMSO was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid-crystalline properties with a number of experimental techniques. Poly(pyridinium salt) with tosylate as a counterion had a crystal-to-smectic phase transition at 116degreesC that persisted up to its decomposition temperature. The corresponding polymer with triflimide as a counterion had not only lower crystal-to-smectic phase transition at 80degreesC but also a smectic-to-isotropic transition at about 180degreesC. Both of these transitions were well below its decomposition temperature. It had better thermal stability than that of the corresponding tosylate polymer. Their fluorescence property in solutions of tetrahydrofuran and methanol as well as in the solid state was also included in this study.