A series of Pb–Na alloys were synthesized by adding sodium to lead. Linear sweep voltammetry (LSV), cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and other analytical methods were used to investigate the electrochemical performances of the Pb–Na alloys in 1.28gcm−3 H2SO4 solution. The results indicate that the addition of sodium reduces the generation of PbO and PbSO4 greatly during anodic process, inhibits the oxygen evolution reaction and accelerates the evolution of hydrogen, and the Pb–Na alloys have good cycle performance and corrosion resistance properties. The alloys retain the merits, whilst removing the flaws, of the pure grid, thereby providing a promising positive grid alloy for spirally wound lead acid batteries.