Experiments were performed to determine crystallization of Fe,S-melts (pyriti≿ and troilitic with molar ratio S/Fe ratios of 2 and 1, respectively) containing traces of gold and silver at (Ag/Au)wt ratios varying from 10 to 0.1. The solid products were studied by optical microscopy, scanning electron microscopy, X-ray powder diffraction (XRD), microprobe analysis, and X-ray photoelectron spectroscopy (XPS) in order to reveal the concentration limits of “invisible” gold and silver in magmatic iron sulfides, and to determine the influence of sulfur on forms of precious metals in the Fe–S system with different Ag/Au ratios.