The corrosive electrochemistry of jamesonite was studied by cyclic voltammetry. Every peak in voltammograms was identified through thermodynamic calculation. The results show an irreversible electrode process by the strong adsorption of oxidation elemental sulfur on jamesonite. A deficient-metal and sulfur-rich compound is formed under the potential of 80 mV at pH 6.86. The passive action by elemental sulfur occurs from 80 to 470 mV and S₂O₃²⁻, SO₄²⁻are produced at potential over 470 mV. The anodic peak producing SO₄²⁻is inhibited due to the deposition of PbSO₄at higher potential in Na₂SO₄solution. The corrosive action of jamesonite becomes strong and the redox characterization similar to PbS, FeS and Sb₂S₃appears at pH 9.18.