An electrochemical study of galena concentrate in perchlorate medium at pH 0 was carried out using carbon paste electrode-galena (CPE-galena). It has been reported that anodic dissolution of galena is inhibited by the formation of elemental sulfur Oil the mineral. Electrochemical characterisations of sulfur species performed in this work complement the results previously reported. Using the cyclic voltammetry technique it was determined that for E < 0.6 V vs. SCE, elemental sulfur and Pb(II) were produced, whereas for E > 0.6 V vs. SCE, thiosulfate and sulfate ions were produced. Through voltammetric characterisation of the species produced in the interface after microclectrolysis at constant potential, the presence of elemental sulfur and PbS2O3 and PbSO4 species was detected. Chronoamperometric studies showed that elemental sulfur on the galena surface inhibits the electrodissolution of this mineral concentrate, emphasising that the presence of Pb(II) ion in the interface gives a greater porosity to the formed film. In addition, it was demonstrated that thiosulfate and lead sulfate species are also porous and only partially inhibit the electrodissolution of galena.