Even though platinum group elements (PGE) solubilities are measured relative to pure metals, the PGE are assumed to dissolve as oxide complexes in silicate melts. PGE-oxide phases are, however, not known in magmatic rocks; in many cases PGE are associated with discrete magmatic phases (alloys, arsenides, bismuthotellurides, antimonides and sulfides). Here, we determine the concentrations of Pt, Pd, S, As, Se and Te in basaltic melts saturated with Fe, Pt or Pd sulfides, arsenides, selenides and tellurides and note that the solubilities of these elements are largely variable and depend on the metal–ligand reservoir in equilibrium. We equilibrated basaltic melts with immiscible Fe, Pt, and Pd sulfide, arsenide, selenide and telluride melts in a piston cylinder apparatus at 1250 °C, 0.5 GPa and relative fO2 of ~ FMQ to FMQ-1.5. The concentrations of S, As, Se and Te in the basaltic melt vary considerably with the metal–ligand reservoir; the highest concentrations are recorded when the ferrous iron cation is the principal metal ligand. When instead Pt-(S/As/Se/Te) or Pd-(S/As/Se/Te) are used, the concentrations of S, As, Se and Te fall drastically. Platinum and Pd increase the activities of semimetals and chalcogenes in the silicate melt more than Fe does. Implications are that Pt and Pd can preferentially form stable associations (fundamental building blocks) with chalcogens and semimetals before the melt attains saturation in Fe-chalcogens or Fe-semimetals. Estimated concentrations of Pt–ligand and Pd–ligand required to saturate silicate melts in some Pt–ligand and Pd–ligand minerals are close to their abundances in the parent magmas of some layered intrusions.