Aluminide coatings on Ni-base superalloys offer resistance to oxidation and hot corrosion at elevated temperatures. Complex depositional and subsequent diffusional interactions of the coating with the substrate result in a multiphase product consisting primarily of β-NiAl and γ′-Ni 3Al intermediate phases. An understanding of interfacial stability between the coating and the substrate is therefore necessary in order to explain the formation of such phases. The Ni-Cr-Al system serves to simplify the complex chemistry of most Ni-base superalloys. In this study, reaction diffusion and interfacial stability were investigated in solid-solid diffusion couples, consisting of a common β-Ni50Al end-member and a series of γ-pure Ni, binary Ni-Cr, and ternary Ni-Cr-Al alloys, isothermally annealed at 1150°C for 49 hours. The morphological development of the interface was examined using optical metallography and quantitative information obtained using electron-probe microanalysis. A transition from a stable or planar to an unstable or nonplanar interface in the β-γ diffusion couples was observed with the systematic variation in Cr content of the γ end- member. Interface breakdown in the β-γ couples was explained by means of microstructural information gathered about interfaces, measured diffusion paths, and a knowledge of phase constitution relationships.