The interaction of aqueous solutions bearing platinum-group elements (PGEs) with sulfides is important for understanding the formation and weathering of PGE ore deposits, mineral processing, and synthesis of nanomaterials. Here, the surface species formed upon the contact of the main sulfide minerals (pyrite, pyrrhotite, galena, chalcopyrite and valleriite) with the solutions of H₂PtCl₆ (pH 1.5, 20 °C) have been studied using X-ray photoelectron spectroscopy (XPS). Uptake of Pt increased gradually with increasing interaction time, and depended, as well as the composition of immobilized products, on the mineral nature and the state of its surface, e.g., the chemical pre-treatment. The highest rate of Pt deposition was observed on galena and valleriite and the lowest on pyrite and pyrrhotite. The preliminary moderate oxidation of pyrrhotite promoted Pt deposition, which, however, was hindered under harsh reaction conditions. The pre-oxidation of pyrite in all cases resulted in a decrease of the Pt deposition. Initially, Pt(IV) chloride complexes adsorb onto the mineral surface, and then the reduction of Pt(IV) to Pt(II) and substitution of chloride ions with sulfide groups occur forming sulfides of Pt(II) and then, Pt(IV). The reduction of Pt species to the metallic state was observed at valleriite after 24 h, probably due the negative charge of the sulfide nanolayers of this sulfide-hydroxide composite mineral.