Metal sulphides are usually semiconductor and their electrical conductivity is low; therefore they are sources of electrons and promote electrochemical reactions. This phenomenon is of significant importance in sulphide flotation. The formation of a hydrophobic surface on the sulphide minerals is the result of various electrochemical reactions. Potential difference in the mineral-liquid interface plays an important role in the kinetics of the reactions, and consequently, on the flotation behaviour of sulphides. The value of the potential difference is influenced by different oxidation-reduction reactions at the interface area, and is measured by a two-electrode system in which an electrode is applied as reference electrode. In this study,we attempted to measure opencircuit potentials of pyrite, pyrrhotite, and steel electrodes with respect to the reference electrode. To verify the results, two reference electrodes, saturated calomel and gold, were used. Timepotential relations with respect to both reference electrodes show that the potential of both pyrite and pyrrhotite increases with time; however, this trend decreases for steel except when at pH 12. The results show a potential drop by an increase in pH value, except for steel, for which the opposite holds. This paper discusses galvanic interactions between minerals and grinding media in the grinding circuits, as well as among other minerals in the flotation processes.