Several novel poly(pyridinium salt)s with heterocyclic pyridine moieties in their backbones with tosylate and triflimide counterions were prepared by either ring-transmutation polymerization reaction of phenylated-bis(pyrylium tosylate) with isomeric pyridine diamines of 4-phenyl-2,6-bis(4-aminophenyl) pyridine in dimethyl sulfoxide (DMSO) for 48 h at 130140 degrees C or by metathesis reaction of the respective tosylate polymers with lithium triflimide in DMSO at about 60 degrees C. Their chemical structures were characterized by FTIR, H-1, C-13 NMR spectroscopy, and elemental analysis. Their number-average molecular weights (M-n) were in the range of 8,000-51,000 and their polydispersities in the range of 1.18-2.13 as determined by gel permeation chromatography. They had excellent thermal stabilities of 340-458 degrees C and high glass transition temperatures > 200 degrees C. As they showed good solubilities in common organic solvents, their solution properties were also characterized for their lyotropic liquid-crystalline properties with polarizing optical microscopy (POM) studies. Their photoluminescent properties were examined by using a spectrofluorometer in both solution and solid states. Their quantum yields were rather low, which were in the range of 1.3-2.0%. Additionally, hand-drawn fibers from the melts were examined to determine their morphologies with a number of microscopic techniques including POM, scanning electron microscopy, and transmission electron microscopy. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4408-4418, 2010