A new chalcogenide-alkali metal alloy of Se80Te8(NaCl)12 has been prepared by a melt-quench technique. The crystallized phases due to the thermal annealing are observed by X-ray diffraction of the powdered sample. The glass transition and kinetics of crystallization in the Se80Te8(NaCl)12 alloy are studied using the differential scanning calorimetric technique under non-isothermal conditions. The activation energy of the glass transition is evaluated by Kissinger and Mahadevan methods. The crystallization activation energy (Ec) is calculated by isoconversion Friedman methods. The decrease of Ec with increasing crystallization conversion is attributed to the complex mechanism of the crystallization process. Based on the shape of the characteristic kinetic function, the crystallization growth is found to be a three-dimensional growth from the bulk nuclei. The results show that the conditions of the Sestak–Berggren model are satisfied for describing the crystallization process of the studied Se80Te8(NaCl)12 alloy. The parameters M and N involved in this model are calculated and related to the crystallization process.