Polysulfone main chains have been functionalized with hypersulfonated aromatic side chains where the suffonic acid groups were highly concentrated on a local scale, with two acid groups placed on the same aromatic ring. This molecular design was implemented to promote the nanophase separation that takes place in proton-exchange membranes between the hydrophobic polymer main chain and the hydrophilic ionic groups responsible for the water uptake and conduction. Morphological investigations revealed that polysulfones functionalized with disulfonaphthoxybenzoyl or trisulfopyrenoxybenzoyl side chains contained larger and more uniform ionic clusters, as compared to conventionally sulfonated polysulfones where the acid groups are dispersed along the main chain. Membranes based on the polymers carrying hypersulfonated side chains formed efficient networks of water-filled nanopores upon hydration, which facilitated excellent levels of proton conductivity exceeding that of the commercial Nafion membrane at moderate water uptakes.