Abstract Thermal dehydrogenation kinetics of sodium alanate (NaAlH 4 ) has been studied with respect to ZrCl 4 additive, and the results were compared with pure NaAlH 4 . The FTIR analysis has shown insignificant effects of ZrCl 4 on the structural integrity of AlH 4 − anion after ball milling. Partial reduction of ZrCl 4 has been observed during ball milling with NaAlH 4 . The in - situ reduction favors to homogeneous and adherent dropping of ZrCl 4 over the NaAlH 4 surface which leads to remarkably improved dehydrogenation process. The dehydrogenation of ZrCl 4 doped NaAlH 4 occurred in three steps similar to pure NaAlH 4 . The dehydrogenation temperatures of all the steps were substantially decreased as compared to pure NaAlH 4 . The apparent activation energy of dehydrogenation of ZrCl 4 doped NaAlH 4 was evaluated for all the dehydrogenation steps and found to be significantly less with respect to pure NaAlH 4 .