A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol 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. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a high-order smectic phase or a low-order smectic phase. Each of them also exhibited a smectic-to-isotropic transition. The ranges of the liquid-crystalline phase were 80-88 degreesC for viologen polymers with tosylate as a counterion and 120-146 degreesC for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288-329 degreesC for viologen polymers with tosylate as a counterion and 343-350 degreesC for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4'-bipyridinium and p-xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum (lambda(max) = 265 nm), an excitation spectrum (lambda(ex) values = 357,443, and 454 with monitoring at 533 nm), and an emission spectrum (lambda(em) = 536 nm with excitation at 430 and 450 nm) in methanol.