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In this work, we have determined by differential scanning calorimetry the values of the glass transition temperatures in the GexTe1—x—ySby (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.05) vitreous system. It is shown that the Gibbs‐Di Marzio modified equation proposed by Sreeram et al. describes the variation of the glass transition temperature with the average coordination number of these high Te‐containing alloys only if data are grouped for each Te content.