Optical absorption and photoluminescence spectroscopy have been carried out on a new class of (phenylene) ring substituted p-pyridylvinylenephenylenevinelyne polymers used as active materials in light emitting diodes. The effects of the ring substitutions on the optical absorption and photoluminescence energies are qualitatively explained through the use of semiempirical quantum chemical modeling of the ring torsion angles. Reduced aggregation through the use of "strap" substituents on the phenylene rings also is discussed.