In this article, x-ray photoelectron spectroscopy (XPS) spectra of iron chalcogenides, FeS, Fe7S8, and Fe7Se8are presented. FeS (troilite) and Fe7S8(pyrrhotite) are among the most common iron compounds on earth. FeS is antiferromagnetic below the Néel temperature ofTN=593–598 K. AboveTα=420 K, FeS is a metal with an NiAs-type crystal structure, but becomes an insulator with a narrow band gap of 0.04 eV belowTα. This transition known as theα-transition is accompanied by a small displacement of the Fe and S atoms from the regular NiAs-type structure. Fe7S8and Fe7Se8are ferrimagnetic metals with Néel temperatures ofTN=578 and 423–460 K, respectively. The crystal structures of Fe7S8and Fe7Se8are derived from the NiAs-type one by introducing ordered Fe vacancies. The polycrystalline samples were synthesized by the Bridgman method. Clean surfaces were obtained by scrapingin situwith a diamond file. All the XPS spectra of the iron chalcogenides are taken at room temperature.