Sulfonated poly(arylene ether sulfone) (SPAES)/polystyrene(PS) and SPAES /polystyrene sulfonic acid (PSSA) composite membranes were studied for a proton-exchange membrane used in a fuel cell. PS microspheres were synthesized by emulsion polymerization. PSSA microspheres with 5.3 mmol/g ion-exchange capacity (IEC) were prepared by sulfonation of PS microspheres. The composite membranes were prepared by solution casting. SPAES/PSSA composite membranes showed higher proton conductivity than a SPAES membrane because of the IEC improved by adding PSSA. Although the addition of PSSA also brought about the increase of a methanol permeability, the proton/methanol selectivity defined as the ratio of the proton conductivity to the methanol permeability was improved at low humidity by adding 5 wt % of PSSA microspheres. Differential scanning calorimetry results indicated that the amount of free water varied in the cases of the addition of the two kinds of organic microspheres. (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 109: 3739-3745, 2008.