Hydrophilic/hydrophobic block copolymers as proton exchange membranes (PEMs) has become an emerging area of research in recent years. These copolymers were obtained through moderate temperature (similar to 100 degrees C coupling reactions, which minimize the ether-ether interchanges between hydrophobic and hydrophilic telechelic oligomers via a nucleophilic aromatic substitution mechanism. The hydrophilic blocks were based on the nucleophilic step polymerization of 3,3'-disulfonated, 4,4'-dichlorodiphenyl sulfone with an excess 4,4'-biphenol to afford phenoxide endgroups. The hydrophobic (fluorinated) blocks were largely based on decafluoro biphenyl (excess) and various bisphenols. The copolymers were obtained in high molecular weights and were solvent cast into tough membranes, which had nanophase separated hydrophilic and hydrophobic regions. The performance and structure-property relationships of these materials were studied and compared to random copolymer systems. NMR results supported that the multiblock sequence had been achieved. They displayed superior proton conductivity, due to the ionic proton conducting channels formed through the self-assembly of the sulfonated blocks. The nano-phase separated morphologies of the copolymer membranes were studied and confirmed by atomic force microscopy. Through control of a variety of parameters, including ion exchange capacity and sequence lengths, performances as high, or even higher than those of the state-of-the-art PEM, Nafion, were achieved. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1038-1051, 2009