Novel main-chain-type and side-chain-type sulphonated poly(ether ether ketone)s (MS-SPEEKs) are synthesised by reacting the sulphonic acid groups of pristine SPEEKs with 2-aminoethanesulphonic acid to improve the nano-phase separated morphology of the material. (1)H NMR and FT-IR spectroscopy are employed to determine the structure and composition of main-chain-type and side-chain-type sulphonated polymers. Flexible and tough membranes with reasonable thermal properties are obtained. The MS-SPEEKs show good hydrolytic stability, and water uptake values ranging from 15% to 30% are observed. Compared to Nafion 117 (R), the methanol permeability of the MS-SPEEKs is dramatically reduced to 8.83 x 10(-8) cm(2) s(-1) to 3.31 x 10(-7) cm(2) s(-1). The proton conductivity increases with increasing temperature, reaching 0.013-0.182 S cm(-1). A maximum power density and open circuit voltage of 115 mW cm(-2) and 0.830 V are obtained at 80 degrees C, respectively, which is significantly greater than the values generated with Nafion 117 (R). The introduction of pendent side-chain-type sulphonic acid groups increases the single-cell performance by more than approximately 20%; thus, the lower water diffusivity, methanol permeability, electro-osmotic drag coefficient and high cell performance indicated that MS-SPEEK is a promising candidate for DMFC applications. (C) 2011 Elsevier B.V. All rights reserved.