The relative stability of Al₁₁Sm₃ (Al₄Sm) intermetallic phases was experimentally investigated through a series of heat treatments followed by microstructural, microchemical, and X-ray diffraction (XRD) analyses. The principal findings are that the high-temperature tetragonal phase is stable from 1655 to 1333 K and that the low-temperature orthorhombic phases, α and γ, have no range of full stability but are metastable with respect to the crystalline Al and Sm reference states down to 0 K. Thermodynamic modeling is used to describe the relative energetics of stable and metastable phases along with the associated two-phase mixtures. Issues regarding transition energetics and kinetics are discussed.