AbstractWe investigated the material properties of different crosslinked sulfonated poly(aryl ether ketone) membranes, focusing on the effect of the degree of sulfonation and crosslinking density on the water uptake, the physical state of the water, and the pore size distribution within the membranes. We observed that the degree of sulfonation and, in particular, the ion‐exchange capacity (IEC) had less effect on the control of the extent of water absorbed than the crosslinking density of the membranes. Crosslinking also enabled the membranes to reach a higher water contents without losing mechanical integrity. Moreover, increasing the crosslinking density resulted in the presence of more bound water, without dissolution of the membrane. The crosslinked membranes had lower methanol permeability and electroosmotic drag values. Only at low IEC values and low water uptake in partially crystalline sulphonated poly(ether ether ketone), SPEEK could the presence of nanometer pores in the water‐equilibrated crosslinked membranes be confirmed by thermoporometry and the pore size distributions were then comparable to those reported for Nafion membranes. At higher IEC values, the water uptake was extremely high, up to 300%, and then the structure of the swollen membranes was more analogous to that of a dilute aqueous solution of the sulfonated polymer, and no nanopores were present. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013