We have been able to determine the deviations from stoichiometry of mercuric iodide (HgI 2) by using differential scanning calorimetry (DSC). Mercury excess or iodine deficiency in mercuric iodide can be evaluated from the eutectic melting of α-Hgl 2-Hg 2I 2 at 235 °C, which appears as an additional peak in DSC thermograms. I 2 excess can be found from the existence of the I 2-α-HgI 2 eutectic melting at 103°C. An additional DSC peak appears in some samples around 112°C, that could be explained by the presence of iodine inclusions. Using resonance fluorescence spectroscopy (RFS) we have been able to determine the presence of free I 2 that is released by samples during the heating at 120 °C (crystal growth temperature), thus giving additional support to the above DSC results.