Thermal dehydrogenation kinetics of sodium alanate (NaAlH4) has been studied with respect to ZrCl4 additive, and the results were compared with pure NaAlH4. The FTIR analysis has shown insignificant effects of ZrCl4 on the structural integrity of All-Li anion after ball milling. Partial reduction of ZrCl4 has been observed during ball milling with NaAlH4. The in-situ reduction favors to homogeneous and adherent dropping of ZrCl4 over the NaAlH4 surface which leads to remarkably improved dehydrogenation process. The dehydrogenation of ZrCl4 doped NaAlH4 occurred in three steps similar to pure NaAlH4. The dehydrogenation temperatures of all the steps were substantially decreased as compared to pure NaAlH4. The apparent activation energy of dehydrogenation of ZrCl4 doped NaAlH4 was evaluated for all the dehydrogenation steps and found to be significantly less with respect to pure NaAlH4. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.