Lead-silver alloys have been extensively used as anode material for the nonferrous metal electrowinning. In the electrowinning process, the electrolyte is usually sulfuric acid solution, and the oxygen evolution reaction take places at the anode, which leads to the corrosive and oxidizing conditions. There are some challenges when conventional lead and lead alloy anodes are used for electrowinning. One is that high oxygen evolution overpotential increases the cell voltage and leads to a low electrowinning efficiency. Besides, the severe corrosive environment caused by acidic electrolytes extremely reduces the service lifetime of the lead anode and promotes lead contamination in the cathode and environment. With increasing requirements for anode service life, energy conservation, environmental protection and product quality, the demand for anode materials with high corrosion resistance and low oxygen evolution overpotential is becoming increasingly urgent. This study constructs an anode alloy by adding Al element into Pb-1wt.%Ag alloy. The zinc electrowinning experiments, microstructure characterization, and electrochemical performance testing have been carried out with the developed Pb-Ag-Al alloy and the widely used Pb-1wt.%Ag alloy. The results indicate that the addition of Al into Pb-Ag alloy modifies its solidification pathway, significantly refines the Ag-rich eutectic phase and promotes the formation of spherical or near-spherical core/shell (Ag, Al)-rich particles. Compared to the Pb-Ag alloy anode which has been widely used in industry, the Pb-Ag alloy with Al addition not only enhances the corrosion resistance, but also reduces its oxygen evolution overpotential. When the Pb-Ag-Al alloy is used as anode for 120 h electrolysis, the generation rate of anode slime is decreased by about 69.5%, and the lead content in the electrolyte and zinc product are decreased by about 14.3% and 61.8%, respectively. Besides, the oxygen evolution potential of Pb-Ag-Al alloy decreases by approximately 0.023 V. The underlying mechanism of Al addition were clarified by microstructure characterization and electrochemical tests. It demonstrates that a thin and dense Al₂O₃ protective film forms during zinc electrodeposition process when the Pb-Ag-Al alloy is used as anode material, which is responsible for the improvement of corrosion resistance performance and the reduction of anode slime. The formation of spherical or nearly spherical (Ag, Al)-rich phase and the transformation of PbSO₄ to active PbO₂ phases in the oxide layer increase the catalytic activity of the alloy, and thus reduces its oxygen evolution overpotential.