The oxidation reactions of ArSb [Ar = 2,6-(HC=N-t-Bu)2C6H3] with S8, grey Se and Te as well as E2Ph2 (E = S, Se, Te) are demonstrated. The reactions of ArSb with elemental sulfur and selenium occurred at elevated temperatures and yielded ArSbE (E = S, 1; Se 2), whereas the reactions with E2Ph2 proceeded at room temperature with subsequent formation of the corresponding insertion complexes ArSb(EPh)2 (E = S 3; Se 4). In addition, ArSb(TePh)2 (5) was formed at very low temperature and showed a temperature-dependent reversible equilibrium with ArSb and Te2Ph2 between –80 °C and 20 °C. The formation and structure of compounds 1–4, which were isolated in good yields, are assigned through multinuclear NMR (1H, 13C, 77Se), IR spectroscopy and microanalyses data. In addition, the molecular structures of 2–4 are further confirmed by single crystal X-ray diffraction studies.