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 α-PbO via discharge of a Pb-O2 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 α-PbO. The mother liquid after crystallization can be recycled for the next batch. The obtained PbO mixed with 60% Shimadzu PbO is superior to the pure Shimadzu PbO in discharge capacity and cycle ability.