Sulfonated polyarylenethioethersulfone (SPTES) copolymers with high proton conductivity (100-215 mS/cm at 65 degrees C, 85% relative humidity) are promising potential proton exchange membrane (PEM) for fuel cells. Small angle neutron scattering (SANS) of the hydrated SPTES copolymer membranes at 25 degrees C exhibit a nanostructure which can be approximated by correlated polydisperse spherical aggregates containing water molecules with liquid-like ordering (Percus Yevick approximation) and large scale water pockets. The ionic domain radius and the volume packing density of the aggregates present in the hydrated SPTES copolymer membranes at 25 degrees C increased with increasing degree of sulfonation. SPTES-80 with highest degree of sulfonation (71.6%) showed a Guinier plateau at the very low q range (q < 1 x 10(-4) 1/angstrom) indicating presence of isolated large scale morphology (R(g) = 1.3 +/- 0.18 micron). The radius of spherical ionic aggregates present in the hydrated SPTES-50 and SPTES-60 copolymer membranes increased with increasing temperature to 55 degrees C, but the large scale morphology changed to a fractal network. Further increase of the sulfonation degree to 63.3% and 71.6% (SPTES-70 and SPTES-80) resulted in a substantial morphology change of the spherical aggregates to an irregular bicontinuous hydrophobic/hydrophilic morphology for the hydrated SPTES-70 and SPTES-80 copolymer membranes at 55 degrees C. Presence of ionic maxima followed by a power law decay of -4 for SPTES-70 and SPTES-80 copolymer membranes was attributed to the bicontinuous phase morphology at high degree of sulfonation and elevated temperature (55 degrees C). The disruption of the larger scale fractal morphology was characterized by significant decrease in the intermediate scattering intensity. Hydrophobic and hydrophilic domains were separated distinctly by sulfonic groups at the interface showing as power law decay of -4 for all hydrated SPTES copolymers. (C) 2011 Elsevier Ltd. All rights reserved.