A series of soluble poly(arylene ether)s containing the phenylphosphine oxide moiety were synthesized by the polymerization of substituted oligophenylene diols with bis(fluorophenyl)phenylphosphine oxide. These amorphous polyethers had well-defined structures and showed blue photoluminescence combined with good thermal stability, especially when phenyl or ethoxy side groups were used. The glass-transition temperatures increased when the size of the oligophenylene segment increased from three to five rings or when the length of the alkoxy substituents decreased. Polymers with glass-transition temperatures up to 270 degreesC were obtained. The absorption and photoluminescent spectra shifted to longer wavelengths with an increase in the oligophenylene block. A redshift was also observed on photoluminescent spectra in the transition from solution to the solid state.