The influence of interaction between mineral components in natural mixtures on the adsorption of organic and inorganic species on the mineral surfaces is recognized. However, the surface phenomena have been meagerly investigated. In this study the formation of different surface species of surfactant (amyl xanthate, C5H11OC(S)S-) adsorbed on FeS2, PbS, and CuFeS2 has been spectroscopically investigated in single-mineral and complex systems. The type and amount of adsorbed species were determined directly on each mineral surface by infrared external reflection spectroscopy. Galvanic interaction between grains of different minerals could have tremendous consequence on the adsorption of surfactants on each mineral component and their future reactivity. The detected changes are dramatic, from no adsorption to the formation of several layers of hydrophobic or hydrophilic surface products depending on which minerals are in contact. It has been documented that even very short contact time between different mineral grains by collision is sufficient to produce dramatic modification of the surface composition and structure. The results obtained indicate clearly that the observations and conclusions aboutthe surfactant adsorption made in a single mineral system cannot be simply extrapolated to describe the real situation in natural multicomponent mineral systems. The obtained information on sulfide mineral interaction in complex systems is indispensable to understand processes taking place in nature at mineral-water interfaces (dissolution of heavy metals). An additional benefit is the improved ability to design efficient separation processes of these minerals.