The aim of this study was to improve the understanding of the deleterious effect of sulfur impurities on the adherence of the thermally-grown oxide on the boundary layer in thermal-barrier-coating systems. In Part I, the sulfur segregation on the free surface of NiAl(001) and at different interfaces between metal and transient alumina scales has been characterized by AES, XPS and LEED. The sulfur diffusion coefficient in the alloy has been determined (D = 0.15 exp(−218,000/RT) cm2/s). It is by three orders of magnitude larger than the nickel and aluminum self-diffusion coefficients. It has also been observed that the sulfur de-segregates upon Al enrichment of the metallic surface. The saturation of the metallic surface with an amorphous alumina layer formed at room temperature blocks the segregation of S. However, in the initial stages of oxidation where the transient θ-alumina grows by cationic transport and inject vacancies at the interface, S segregates at the interface between the alumina thin films and the metallic substrate.