New polyethers containing alternating conjugated segments of p-terphenyl or p-quinquephenyl with p-styrylbenzene side groups and aliphatic spacers were synthesized with pyrylium salts. They had moderate molecular weights, were amorphous, and dissolved in tetrahydrofuran, chloroform, and other common organic solvents. The glass-transition temperatures were 68-82 and 110-153 degreesC for the polymers that carried p-terphenyl and p-quinquephenyl moieties, respectively. The absorption spectra showed a peak around 325 nm, and the band gaps were 3.27-3.34 eV, which were calculated from the onset absorption in solution. The photoluminescence maxima were at 393-398 nm in solution and 422-449 nm in thin films, indicating that the polymers were violet-blue-emitting materials. The photoluminescence quantum yields in solution were up to 0.25. The polymers displayed both in concentrated solutions and in the solid state intramolecular or intermolecular interactions. The polarity of the solvent influenced the shape of the photoluminescence curve.