The electrochemical behavior of lead, lead–antimony, and lead–calcium–aluminium–tin alloys has been studied in solutions containing various concentrations of sulfuric and phosphoric acids. The dependence of these electrode processes on some experimental conditions (mainly sweep rate and potential range) has been studied. The measurements were performed using a cyclic voltammetry technique. The study and the analysis of the morphology of alloys have been performed using a scanning electron microscope (SEM). Cyclic voltammograms of the lead–antimony alloy electrodes, similarly to pure lead electrode, also show the “anodic excursion” peak under some experimental conditions. Well defined current waves, corresponding to the oxidation and reduction processes of Sb, are observed, if the alloy surface is freshly abraded. The oxidation of antimony starts at potentials at which the formation of PbO takes place. The peak current of Sb oxidation reaction decreases during successive cycles, suggesting that Sb dissolves from the alloy surface during the first CV sweeps. Another explanation for this effect might be the formation of a PbSO4 selective membrane.