A series of sulfonated poly(arylene ether phosphine oxide)s (sPAEPO) were prepared by direct poly-condensation of sulfonated bis(4-fluorophenyl)phenyl phosphine oxide and bis(4-fluorophenyl)phenyl phosphine oxide with various diphenol-type monomers. The resulting ionomers show high molecular weight and excellent thermal stability. The bisphenol moieties of sPAEPO greatly affect the properties. sPAEPO-NA, -Bis A, -BP, and -6F show excellent dimensional stability. However, sPAEPO-DB and -HQ indicate abrupt swelling even at 80 and 90 C. respectively. unsuitable for proton exchange membranes. In contrast, sPAEPO-6F with the lowest swelling exhibits the highest conductivity of 7.68 x 10(-2) S cm(-1) among all the sPAEPO, close to that of Nafion 117. Besides, sPAEPO-NA and -Bis A show a worse oxidative stability than other sPAEPO (sPAEPO-Bis A, -BP, -HQ, and -6F) due to the naphthalene ring and the isopropylidene unit in the backbone, respectively. Contrary to sPAEPO-Bis A and -BP, sPAEPO-NA and -6F exhibit well connective ionic domains owing to the high hydrophobic nature or the naphthalene ring and hexafluoroisopropylidene moieties. The connected ionic domains provide sPAEPO-NA and -6F with higher proton conductivity in comparison with sPAEPO-Bis A and -BP. In conclusion, sPAEPO-6F has the best comprehensive properties among all the sPAEPO, indicating a promising prospect in proton exchange membrane applications. (C) 2008 Elsevier B.V. All rights reserved.