Two poly(pyridinium salt)s containing a bulky organic counterion such as 2-naphthalenesulfonate were synthesized by the ring-transmutation polymerization reaction of bis(pyrylium 2-naphthalenesulfonate) with the corresponding aromatic diamines on heating in dimethyl sulfoxide (DMSO) at 145-150 degreesC for 24 h, and characterized for their lyotropic liquid crystalline as well as fluorescence properties in both polar protic and aprotic solvents such as methanol and DMSO. Their polyelectrolyte behavior in DMSO was also determined by solution viscosity measurements.