Polymer electrolyte membranes (PEMs) made of sulfonated poly(arylene ether)s consisted of 3,3'-disulfo-4,4'-dichlorodiphenylsulfone disodium salt, 2,6-dichlorobenzonitrile, and one of three dihydroxynaphthalene isomers (2,6-, 2,7-, and 1,5-dihydroxynaphthalene, abbreviated as 2,6-N, 2,7-N, and 1,5-N, respectively) were prepared with similar level of inherent viscosity and ion exchange capacity, and structural effect of the catenation in dihydroxynaphthalene isomers on membrane properties was compared. In the case of membranes for PEM fuel cell application with relatively high ion exchange capacity around 2.1 mequiv/g, three copolymers showed almost the same proton conductivity; however, swelling in water increased with the following order: 1,5-N < 2,6-N < 2,7N. In the case of direct methanol fuel cell membranes with lower ion exchange capacity around 1.5 mequiv/g, no remarkable difference in proton conductivity was also observed in three isomeric copolymers and swelling property and methanol permeability were lower in 1,5-N and 2,6-N copolymers than 2,7-N copolymer. These tendencies show that higher rigidity or energy barrier for conformational change of polymer chain gives better performance of PEM for fuel cells with superior dimensional stability.(C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012