NiAlFe thin films were prepared onto sapphire single crystals by physical vapour deposition (PVD) and these were analysed by X-ray photoelectron spectroscopy (XPS) in combination with argon ion etching to determine the composition depth profile and interfacial characteristics of the samples. Non-linear least square fitting (NLLSF) analysis of the data was required due to the conflict of several peaks of interest. XPS depth profiles show that, for non-annealed NiAlFe-Al2O3, the interface is sharp and oxygen diffusion occurs at different annealing temperatures. Ni remains chemically unaffected by the presence of oxygen while the formation of aluminium oxide compounds occur. Two iron species are present in the film thickness where the low binding energy component is attributed to Fe-Fe or Fe-Al interactions and the higher one to the NiAlFe compound. The reduction-dissolution of the sapphire substrate leads to depletion of oxygen in the sapphire surface layer and the formation of alumina at the NiAlFe-Al2O3 interface. Within the film, aluminium and nickel are present as an intermetallic compound. Annealing of the samples induces surface oxidation and the subsequent formation of an Al2O3 layer. This type of interphase morphology should lend to optimal fibre/matrix (F-Mj adhesion, and therefore optimal load transfer between the matrix and reinforcement.