A new anion exchange membrane was synthesized by a green and facile route-chemically grafting polybenzimidazole (PBI) membrane with BrCH(2)CH(3). The obtained membrane was characterized by means of ex-situ and in-situ tests (EDX, FTIR, AC impedance, single cell test and so on). The results suggested that the group of -CH(2)CH(3) was successfully grafted onto N atom within PBI backbone, while with Br(-) as counter ion. The corresponding ionic conductivity and ethanol permeability were about 0.022 Scm(-1) and 5.24 x 10(-8) cm(2)s(-1) respectively. Finally, single cell test suggested that air-breathing alkaline direct ethanol fuel cell with quaternized PBI membrane can deliver a peak power density of about 11 mWcm(-2) even at ambient temperature of 13 degrees C, which was better than those of air-breathing alkaline direct methanol fuel cell in literatures. In addition, a possible reaction mechanism was also proposed and discussed. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.