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The results of X-ray induced photoelectron spectroscopy (XPS) experiments on several phases of the ternary system Tl-Sb-S are reported. The binding energies of the inner S, Sb and Tl electrons increase with increasing quantities of Sb and decreasing amounts of Tl in these compounds. This is explained by the influences of the proportions of the bonded metals on the effective electron affinity of S. The higher proportions of the more electronegative element bonded to S cause the increase of its effective electron affinity. The results for Tl₂S (carlinite), Tl₃SbS₃, TlSbS₂ (weissbergite), TlAsS₂ (lorandite) and Sb₂S₃ (antimonite) can be interpreted in this way. The results for Tl₄S₃ suggest a predominantly covalent character of bonding for both Tl(III) and Tl(I), which are present in this sulfide. From comparison with Tl₃SbS₄ it could be supposed that Tl(III)-S bond has a more covalent character than Sb(V)-S bond. The results for Tl₃SbS₄ are in agreement with crystal structure data and the results of Moessbauer spectroscopy. For AsS (realgar) the binding energies of the inner electrons of As and S significantly increase, showing that the electrons in molecular orbitals are less strongly bonded to individual atoms, as compared to pure elements. The results for the amorphous TlSb₅S₈ (corresponding in composition to parapierrotite) suggest that in amorphous compound the Tl-S bonding is stronger and the coordination of Tl more regular than in a crystalline one. © 1993 Springer-Verlag.