In the present research, a novel bio-electrochemical cell was designed by using a bipolar membrane to separate the anode and the cathode chambers to overcome the thermodynamic barrier for hydrogen production from acetate. By using this configuration, hydrogen could be produced on cathode without the aid of bias potential or photo irradiation. In the designed bioelectrochemical cell, with 0.1 mol L-1 sulfuric acid as catholyte, acetate could be oxidized on bio-anode with additional electricity generated spontaneously. With an external resistance of 400 Omega, the maximum power density of 0.0145 W m(-2) could be achieved. In the present design, the anode efficiency of 3.9% and cathode efficiency of 41% could be obtained, respectively. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.