A new difluoride monomer bilaterally substituted with rigid benzimidazole groups was synthesized efficiently. A series of new poly(aryl ether)s (PAEs) containing benzimidazole pendants were prepared from the novel difluoride monomer with various commercially available aromatic bisphenols using nucleophilic aromatic substitution reaction. All the PAEs show high glass transition temperatures (T (g) > 205 A degrees C), excellent thermal stability (T (d) > 420 A degrees C), and good solubility in common organic solvents.