A cathodic decomposition model was examined for both pyrrhotite and chalcopyrite in an attempt to analyze the formation of surface coatings in deoxygenated solutions at natural, near neutral pH. Combination potentials established between the mineral-grinding media pair were simulated by applying a potential of -0.455 V (vs. a standard hydrogen electrode) either to a pyrrhotite or to a chalcopyrite electrode. Chronoamperometry was used to study the polarization behaviors and alteration of mineral surfaces through cathodic processes. The kinetic parameters of cathodic decomposition of pyrrhotite and chalcopyrite were determined and compared. It was concluded that pyrrhotite decomposed faster than chalcopyrite in near-neutral pH solutions. Both minerals were then covered by a film consisting mainly of iron hydroxides, which adversely affected their flotation.