AbstractThermodynamic properties of liquid Na‐Te solutions were measured over the range 0–52 at.% Na at temperatures between 573 and 873 K by means of alloy concentration cells. Beta alumina was used as the solid electrolyte. The following properties were derived from the emf data: ΔG, ΔH, ΔS, the excess heat capacityCEpand the excess stability, ES. The Gibbs energy, enthalpy and entropy showed marked negative deviations. The plot of excess stability versus composition exhibits a rather flat shoulder between 10 and 20 at.% Na and a broad maximum or shoulder near 50% Na indicating maximum short‐range ordering near these compositions. Liquidus and invariant points on the phase diagram as well as the Gibbs energies of formation of the solid compounds NaTe3, NaTe and Na2Te have also been de