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In this study, polyhedral oligomeric silsesquioxane (POSS) moieties were incorporated into sulfonated poly(ether ether ketone) (SPEEK) to form a new crosslinked proton exchange membrane (PEM).The distribution of the POSS containing cross-linkers with or without sulfonic acid groups dictates the water behavior and connectivity of hydrophilie domains of the PEM.A PEMformed by incorporating 17.5 wt% of the cross-linker (containing POSS macromer and sulfonic acid groups) into SPEEK exhibits high proton conductivity (0.0153 S/cm), low methanol permeability (1.34* 10-7 cm2/s), and high selectivity (1.14* 105 Ss/cm3).