Abstract Reactive Hydride Composites (RHCs), ball-milled composites of two or more different hydrides, are suggested as an alternative for solid state hydrogen storage. In this work, dehydrogenation of 2NaBH 4 + MgH 2 system under vacuum was investigated using complementary characterization techniques. At first, thermal programmed desorption of as-milled composite and single compounds was used to identify the temperature range of hydrogen release. RHC samples annealed at various temperatures up to 500 °C were characterized by X-ray diffraction, infrared spectroscopy and scanning electron microscopy. It was found that the dehydrogenation reaction under vacuum is likely to proceed as follows: 2NaBH 4 + MgH 2 (>250 °C) → 2NaBH 4 + 1/2MgH 2 + 1/2Mg + 1/2H 2 (>350 °C) ↔ 3/2NaBH 4 + 1/4MgB 2 + 1/2NaH + 3/4Mg + 7/4H 2 (>450 °C) → 2Na + B + 1/2Mg + 1/2MgB 2 + 5H 2. In addition, presence of NaMgH 3 phase suggests the occurrence of secondary reactions.