The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 Å, a hydroxide layer of 2–3 Å, and a thickness of the sub-surface alloy layer of 20–35 Å. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr³⁺, Mo^(4,5,6)+, and Nb⁵⁺, while no Ni oxide was detected. The hydroxide layer mainly contained Ni²⁺ and Cr³⁺ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.