Magnesium chloride hex-ammoniate (MgCl2·6NH3) is an intermediate to produce anhydrous magnesium chloride (MgCl2) by method of reaction crystallization. MgCl2·6NH3 is decomposed at 670K to produce anhydrous magnesium chloride. The process of thermal decomposition and its non-isothermal kinetics of MgCl2·6NH3 is studied. Results show that the thermal decomposition process is made up of three stages, the thermal decomposition functions and the thermal decomposition kinetics parameters, such as activation energy (E), pro-exponential factor (A) of MgCl2·6NH3 for each step are obtained by means of the Acher differential, the Coats-Redfern integral and multi-accelerated heating rate method. This study provides a valuable theoretical basis for MgCl2·6NH3 decomposition process on industrialization.