In order to solve the problem of high pollution and high energy consumption of the current lead oxide (PbO) preparation processes, a new clean and energy saving preparation method for high purity alpha-PbO via discharge of a Pb-O-2 fuel cell is reported. The fuel cell with metallic lead anode, oxygen cathode, and 30% NaOH electrolyte can provide a discharge voltage of 0.66-0.38 V corresponding to discharge current range of 5-50 mA cm(-2). PbO is precipitated from the NaHPbO2 containing electrolyte through a cooling crystallization process after discharge process, and the XRD patterns indicate the structure is pure alpha-PbO. The mother liquid after crystallization can be recycled for the next batch. The obtained PbO mixed with 60% Shimadzu MO is superior to the pure Shimadzu PbO in discharge capacity and cycle ability. (C) 2017 Elsevier B.V. All rights reserved.