A novel synthesis of bisbenzils has been investigated and used to prepare several monomers for the synthesis of poly(phenylquinoxaline)s (PPQs). PPQs incorporating 2-naphthalenyl moieties in the pendent position have been prepared. The polymers are amorphous but exhibit excellent resistance to most organic solvents, and are soluble in only m-cresol and concentrated sulfuric acid.