AbstractA mixture of 3NaH/AlB2 was prepared by ball-milling; its hydriding reaction was studied between 375–425 °C and 25–50 bar hydrogen pressure by means of volumetric titration. The hydriding reaction was characterized by means of in situ synchrotron radiation powder X-ray diffraction and high-pressure differential scanning calorimetry. Hydriding reaction took place at the molten state, and its reaction products were NaBH4 and Al. The scanning electron microscopy images of the material revealed that the material morphology changes after hydriding. A maximum hydrogen uptake of 4.7 wt % was registered for the hydriding experiment at 425 °C and 50 bar hydrogen pressure. Dehydriding reaction was studied by means of volumetric titration and differential scanning calorimetry. The dehydriding reaction at 425 °C and 1 bar argon pressure registered a release of 2.4 wt %. The low dehydriding level was attributed to the reduction of the available particle surface upon melting of the material during the hydriding reaction.