A high-performance hydroxide exchange membrane was prepared by the chloromethylation and quatemization of Poly ether ether ketone (PEEK) for microbial fuel cell applications. The study reports on the synthesis of a novel quaternized poly ether ether ketone (QPEEK) membrane and subsequent utilization of the ionomer as an anion exchange membrane (AEM). The structural characterization of chloromethylation and quatemization of PEEK was confirmed by FT-IR and H-1(1) NMR spectroscopy and the morphologies were viewed by scanning electron microscopy. The effects of oxygen crossover and specific substrate crossover on cathode potential were also studied in detail. The investigation of QPEEK with the commercially available AEM (AMI-7001) revealed that the QPEEK shows excellent static properties, i.e. ion-exchange capacity, water uptake, thickness, etc.; and kinetic properties, i.e. diffusion permeability and better durability over 250 days. Power density obtained from an MFC containing the QPEEK-AEM produced higher value (60 W/m(3)) than the commercial AMI-7001 AEM (52 W/m(3)). This study shows that QPEEK could be used as an efficient and a cost effective AEM for an MFC. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.