Composite membranes based on sulfonated poly(aryl ether ketone)s containing the hexafiuoroisopropylidene diphenyl moiety and poly(amic acid) with oligoaniline in the main chain have been prepared and immersed in H(3)PO(4) to obtain acid-doped composite films. As expected, the water uptake values and methanol permeability of the composite membranes decrease with the increase of the weight fraction of PAA in the membrane matrix. Notably, the SPEEK-6F/PAA-15 shows a water uptake of 13.2% and a methanol permeability of 0.9 x 10(-7) cm(2) s(-1), which are much lower than those of the Nafion (28.6% and 15.5 x 10(-7) cm(2) s(-1), respectively). Although the proton conductivities decrease after the addition of PAA, higher selectivity values are obtained with the composite membranes. Therefore, the SPEEK-6F/PAA blend membranes, with the improved proton conductivity, methanol resistance and good thermal stability, can be used as a good alternative for proton conductive membranes with potential application in proton exchange membrane fuel cells (PEMFCs). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.