A new series of sulfonated poly(p-phenylene-co-aryl ether ketone)s (s, m, I-SPP-co-PAEKs) microblock polymers containing different hydrophobic units with precisely defined lengths have been prepared via the nickel (0) catalyzed coupling copolymerization and characterized to act as proton exchange membranes. By controlling the length and chemical structure of the hydrophobic units in the copolymers, these novel microblock polymers can exhibit well-developed nanophase morphologies and large length-scale of the ionic channels, resulting in the improvement of the proton conductivity in both the wet and dry state. Moreover, the membrane I-SPP-co-PAEK 1.80 with the largest hydrophobic micro-block length shows high proton conductivity, excellent dimensional stability, low glass-transition temperature (Tg), good oxidative stability and superior cell performance. (C) 2015 Elsevier B.V. All rights reserved.