This article presented the synthetic and preparation route of quaternary ammonium functionalized anion exchange membranes (AEMs), which were derived from an engineering plastics polymer, poly(arylene ether sulfone) with 3,3,5,5-tetramethyl-4,4-dihydroxybipheny moiety (PAES-TM). The benzylmethyl groups on the main-chain of PAES-TM were converted to the bromomethyl groups via a radical reaction, thereby avoiding complicated chloromethylation, which required carcinogenic reagents. The chemical structure of the bromomethylated PAES was characterized by H-1 NMR spectrum. Following a homogeneous quaternization with trimethylamine in the solution, a series of flexible and tough membranes were obtained by a solution casting and anion exchange process. The ion exchange capacity values were ranging from 1.03 to 1.37 meq g(-1). The properties of the membranes, including water uptake, hydroxide conductivity, and methanol permeability were evaluated in detail. The AEM showed a high conductivity above 10(-2) S cm(-1) at room temperature and extremely low methanol permeability of 4.16-4.94 x 10(-8) cm(2) s(-1). The high hydroxide conductivity of TMPAES-140-NOH could be attributed to the nano-scale phase-separated morphology in the membrane, which was confirmed by their transmission electron microscopy images. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40256.