The standard Gibbs energy of formation of M2TeO6 and M6TeO12 (where M = Sc, Y), was determined from its vapor pressure measurements by employing thermogravimetry-based transpiration technique. This technique was validated by measuring the vapor pressure of well-studied substances such as TeO2(s) and CdCl2(s). The temperature dependence of the vapor pressure of TeO2(g) over the mixtures M6TeO12 + M2O3 (where M = Sc, Y), generated by the incongruent vaporization reaction, M6TeO12(s) → 3M2O3(s) + TeO2(g) + ½O2(g) were measured in the temperature range 1,413–1,473 K and 1,623–1,743 K for Sc6TeO12(s) and Y6TeO12(s), respectively. Similarly, the vapor pressure of TeO2(g) over the mixtures M2TeO6(s) + M6TeO12(s) generated by the vaporization reaction, 3M2TeO6(s) → M6TeO12(s) + 2TeO2(g) + O2(g) was measured in the temperature range (1,223–1,293 K) and (1,333–1,423 K) for Sc2TeO6(s) and Y2TeO6(s), respectively. From the vapor pressure measurements, the standard Gibbs energy of formation of M6TeO12 and M2TeO6 were derived.