Robust hydroxide conducting membranes are required for long-lasting, low-cost solid alkaline fuel cells (AFCs). In this study, we synthesize Nafion-based anion exchange membranes (AEMs) via amination of the Nafion precursor membrane with 1,4-dimethylpiperazine. This initial reaction produces an AEM with covalently attached dimethylpiperazinium cations neutralized with fluoride anions, while a subsequent ion exchange reaction produces a hydroxide ion conducting membrane. These AEMs possess high thermal stability and different thermal transition temperatures compared to Nafion, while small-angle X-ray scattering reveals a similar ionic morphology. The hydroxide ion conductivity of the Nafion-based AEM is fivefold lower than the proton conductivity of Nafion at 80 degrees C and 90% relative humidity. More importantly, the hydroxide conductivity is insensitive to drying and rehydrating the membrane, which is atypical of other AEMs with quaternary ammonium cations. The high chemical and thermal stability of this hydroxide conducting Nafion-based AEM provides a promising alternative for AFCs. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011