Superalloy 690 substrates containing mainly Cr and Ni aluminides on the uppermost surface, formed by atmospheric plasma spraying and heat treatment, were oxidized at 1273 K in air for 2 h. Quantitative X-ray photoelectron spectroscopy (XPS) analyses indicated that the outermost surface layer formed on aluminides is composed of ~21.0 at.% Al⁺³ (as Al₂O₃), 17.0 at.% Al0 (elemental aluminium), 1.4 at.% Cr⁺³ (as Cr₂O₃) and 60.5 at.% O (in Al₂O₃ and Cr₂O₃ and also includes oxygen contaminant). Surface sputtering for 5 min exhibited splitting of Cr2p_3/2 peak into a doublet comprising Cr⁺³ (0.9 at.%) and Cr⁰ (0.4 at.%) with the presence of 1.15 at.% Ni0 in the surface layer that mainly contained ~37.3 at.% Al+3, 7.3 at.% Al⁰ and 52.9 at.% O. Surface sputtering for 15 min indicated surface composition similar to surface sputtered for 5 min but with a marked reduction in ratio of Al⁺³/Al⁰ (32.2 at.% Al⁺³/11.90 at.% Al⁰) in the surface layer.