Study about magnesium sulfate − water vapor equilibrium proved to be very interesting especially on the use of dehydration-hydration reactions for the heat storage application in recent research. Heat is realized by hydration of lower hydrates as this reaction is exothermic. Therefore, reversible reaction, endothermic thermal dehydration of higher hydrates, is used for charging of system and in this state the energy can be stored over long time. Even if magnesium sulfate appears as promising candidate with high theoretical energy density of 2.8 GJ/m⁻³, technological process is rather complicated. The main problem that thermodynamic and kinetic data are poorly understood to present. In these study salt hydrates equilibrium of magnesium sulfate was investigated by new approach. It makes possible to understand the dehydration reaction of MgSO₄·6H₂O for heat storage application. Dehydration reaction under various water vapor pressures and temperatures were investigated by thermogravimetric analysis. The result showed that water content in the solid phase is a function of temperature for given water vapor pressure. So, we can conclude that this magnesium sulfate − water vapor system is bivariant and some hydrates appear as the non-stoichiometric hydrates.