Two series of sulfonated naphthalenic polyimides containing ether and ketone linkages (SPI-KK-X and SPI-K-X) were prepared by a one-pot polymerization reaction of sulfonated diamine monomers, 1,4-bis[3-sodium sulfonate-4-(4-aminophenoxy)benzoyl]benzene or 4,4-bis[3-sodium sulfonate-4-aminophenoxy]benzophenone, with 4,4-diaminodiphenyl ether and 1,4,5,8-naphthalenetetracarboxylic dianhydride. The membranes cast from the resulting polymers had good thermal and oxidative stability, dimensional stability and mechanical properties. At 80 degrees C, the proton conductivities of several samples, including SPI-KK-1, SPI-K-1 and SPI-K-2 were higher than 0.10 S/cm, which were comparable to that of Nafion. Methanol permeabilities of the obtained polymer electrolyte membranes (PEMs) were in the range of 1.43-2.03 x 10(-7) cm(2)/s, which were several times lower than that of Nafion 117. It is interesting to note that the SPI-KK-X series, having a more rigid phenyl-ketone-phenyl-ketone-phenyl moiety, had a lower dimensional swelling ratio and lower methanol permeability in comparison with the corresponding SPI-K-X series at the same level of ion exchange capacity (IEC). (C) 2010 Elsevier B.V. All rights reserved.