Novel poly(arylene ether)s with sulfonic acid groups attached onto pendent biphenyl rings were successfully synthesized by the nucleophilic displacement of aromatic dihalides with bisphenols in aprotic solvent in the present of excess potassium carbonate, followed by sulfonation with chlorosulfonic acid. The sulfonation took place only on the pendent biphenyl rings due to the specially designed molecular structure. The sulfonated polymers were very soluble in common organic solvents, such as dimethyl sulfoxide, N,N'-dimethylacetamide, dimethylformamide, and can be readily cast into tough and smooth films. These membranes showed excellent stabilities resistance to both oxidation and hydrolysis, as evidenced by subjecting to both Fenton's reagent test and immersion in boiling water. The proton conductivities (3.2 x 10(-3) S cm(-1)) of the as-made membranes were higher than that of Nafion (R) 117 (1.9 x 10(-3) S cm(-1)) under same conditions. The satisfied properties of these new polymers demonstrated them as promising candidates for proton exchange membrane in PEM fuel cell applications. (c) 2006 Elsevier B.V. All rights reserved.