Due to the excellent electrical conductivity and mechanical properties, Al/Pb-Ag alloy has a great potential to be used as an alternative anode for zinc electrowinning. In this work, the effects of Ag content and surface plating with β-PbO2 on the anodic behavior and reaction kinetics have been investigated by cyclic voltammetry (CV), anodic polarization curves, electrochemical impedance spectroscopy (EIS) and corrosion rate test. The phase composition and microscopic morphology of the anode oxide layers after electrolysis were observed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results indicate that both increasing Ag content and electroplating β-PbO2 layer contribute to the improvement of oxygen evolution activity, electrocatalytic activity and corrosion resistance of the anodes. Al/Pb-0.75%Ag plating β-PbO2 has the lowest oxygen evolution overpotential followed by that of Al/Pb-0.3%Ag plating β-PbO2, Al/Pb-0.75%Ag and Al/Pb-0.3%Ag. Besides, high content of silver is more benefit to improve corrosion resistance compared with electroplating β-PbO2 on anode. In addition, the phase composition of four anodes layer are mainly composed of α-PbO2, β-PbO2, Pb and PbO.