Abstract: Surfaces of a natural sample of arsenopyrite (FeAsS) were oxidized by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The oxidants used were air during heating to relatively low temperatures (150°C), steam, ammonium hydroxide, hydrogen peroxide, and sulphuric acid. Electrochemical oxidation in water was also undertaken. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and spectral reflectance measurements, were used to characterize the surface compositions. New data are proposed for the binding energies of core electrons in arsenopyrite based on the fitted XPS spectra: 706.9 eV for the Fe 2p^3/2 level, 161.2 eV for the S 2p level, and 40.7eV for the As 3d level. Spectroscopic analyses of the surfaces following oxidation indicated a range of iron oxides and hydroxides (Fe_1−xO, Fe₃O₄, Fe₂O₃, FeOOH and Fe(OH)₃), arsenic oxides (As₂O₃ and As₂O₅), sulphur and iron sulphates (FeSO₄, Fe₂(SO₄)₃). The relative proportions of the different phases present in the surface layer are related to the strength of the oxidant employed and, where relevant, the Eh/pH conditions prevalent during oxidation. The conclusions regarding the nature of the oxidation of arsenopyrite are discussed in relation to arsenopyrite extraction by flotation and leaching, and the breakdown of arsenopyrite in natural systems.