Sodium aluminum hydride has been extensively investigated for hydrogen storage applications whereas its intermediate decomposition compound Na3AlH6 received much less attention, despite having a lower dissociation pressure and a reasonable hydrogen storage capacity of 3.0 wt%. In this work, Na3AlH6 is synthesized through ball milling, starting from NaAlH4 and 2 NaH in the presence of TiCl3 catalyst precursor, and evaluated on its hydrogen sorption properties and cycle stability. Further addition of 8 mol% Al and 8 mol% activated carbon (AC) and their effect on both the hydrogen sorption properties and cycle stability have been investigated. In order to explore whether the introduction of the Al and AC additives would be more beneficial (in terms of hydrogen sorption behavior and cycle stability) after the Na3AlH6 synthesis or during its synthesis, pre-synthesized Na3AlH6-based measurements were also included in this work. TiCl3-catalyzed NaAlH4 + 2 NaH sample showed a stable reversible hydrogen storage capacity of 1.7 wt%, which was further increased to 2.1 wt% with the addition of Al-powder and activated carbon AC.