The kinetics and mechanism of the thermal dehydration of magnesium acetate tetrahydrate were investigated as a typical example of the glass formation process via the thermal decomposition of solids. Formation of an intermediate fluid phase was identified as the characteristic phenomenon responsible for the formation of anhydrous glass. Thermal dehydration from the surface fluid layer regulates the zero-order-like rate behavior of the mass-loss process with an apparent activation energy E-a approximate to 70-80 kJ mo(-1). Because of variations in the mechanism of release of the water vapor with changes in the reaction temperature range, the mass-loss behavior is largely dependent on the particle size of the sample and heating conditions. The formation of hollow anhydrous glass is the novel finding of the present study. The mechanism of formation is discussed in terms of complementary interpretations of the morphological changes and kinetic behavior of the thermal dehydration. On further heating, the as-produced anhydrous glass exhibits a glass transition phenomenon at approximately 470 K with an E-a approximate to 550-560 kJ mol(-1), and subsequently crystallizes via the three-dimensional growth of nuclei controlled by diffusion. The crystallization process is characterized by an E-a approximate to 280 kJ mol(-1) and an enthalpy change Delta H = -13.3 kJ mol(-1), resulting in the formation of smaller, rounded particles of crystalline anhydrate.