A new series of poly(pyridinium salt)s that contained side stilbenyl groups or p-distirylbenzene segments in the main chain were synthesized from the reactions of bis(pyrylium salts) with diamines. They were characterized by viscometry, Fourier transform infrared spectroscopy, NMR, X-ray scattering, differential scanning calorimetry, thermomechanical analysis, ultraviolet-visible analysis, and luminescence spectroscopy. The polymers were amorphous and soluble in polar aprotic solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. The glass-transition temperatures were in the range of 59-123 degreesC. These polymers had initial decomposition temperatures of 240-295 degreesC and afforded anaerobic char yields of 29-53% at 800 degreesC. Both the absorption and photoluminescence (PL) spectra of the polymers were studied, and the PL quantum yields in solution were determined. The polymers showed violet-blue fluorescence in solution with PL maxima at 408-416 nm and violet-green fluorescence in thin film with PL maxima at 454-523 nm. The structure of the diamine utilized for the preparation of the polymers did not influence their PL maxima.