Thermodynamic properties of Nd–Bi and Nd–Sn alloys were determined via electromotive force (emf) measurements at 725–1075 K. The emf measurements of an Nd–Bi alloy at mole fraction xNd = 0.20 were conducted using a solid CaF2–NdF3 electrolyte relative to pure Nd(s). The emf values from the CaF2–NdF3 electrolyte were verified in separate experiments in molten LiCl–KCl–NdCl3 where pure Nd(s) was electrodeposited. The Nd–Bi (xNd = 0.20) exhibited two-phase behavior with a peritectic reaction (L + NdBi = NdBi2) at 926 K from differential scanning calorimetry. The two-phase Nd–Bi (xNd = 0.20) was employed as a stable reference electrode in molten LiCl–KCl–NdCl3 for emf measurements of Nd–Bi (xNd = 0.15–0.40) and Nd–Sn (xNd = 0.10) alloys. The emf measurements of these alloys were reproducible during thermal cycles over 50 h and were used to calculate thermodynamic properties, including the partial molar Gibbs energy, entropy, and enthalpy.