Novel locally sulfonated poly(ether sulfone)s with highly sulfonated units were successfully synthesized for fuel cell applications. Poly(ether sulfone)s were prepared by the nucleophilic substitution of bis(4-fluorophenyl) sulfone with 1,2,4,5-tetrakis([1,1'-biphenyl]-2-oxy)-3,6-bis(4-hydroxyphenoxy)benzene and bis(4-hydroxyphenyl) sulfide, followed by oxidation using m-chloroperoxybenzoic acid. The desired highly sulfonated units were easily introduced by postsulfonation and each one had ten sulfonic acid groups. The sulfonated polymers gave tough, flexible, and transparent membranes by solvent casting. The high contrast in polarity between highly sulfonated units and hydrophobic poly(ether sulfone) units enabled the formation of defined phase-separated structures and well-connected proton paths. The sulfonated polymers exhibited excellent proton conductivity over a wide range of relative humidities. The proton conductivity of the sulfonated polymer with an ion exchange capacity value of 2.38 mequiv/g was comparable to that of Nafion 117 even at 30% relative humidity. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 34443453,2009