The reactivity and thermal decomposition of γ-Mg(BH4)2-MHx, M = Li, Na, Mg, and Ca composites has been examined with the objective of studying the hydrogen storage capability of the composites. The samples were prepared by manual grinding γ-Mg(BH4)2 with a metal hydride to obtain homogenous mixtures. In-situ synchrotron radiation powder X-ray diffraction (SR-PXD) and simultaneous thermogravimetric analysis, differential scanning calorimetry, and mass spectrometry was performed to analyse the decomposition mechanism, whereas solid-state 11B nuclear magnetic resonance spectroscopy and SR-PXD was used to investigate the decomposition products. Interestingly, substitution reactions take place between magnesium borohydride and lithium, sodium and calcium hydride forming the more stable metal borohydrides, M(BH4)x, M = Li, Na or Ca. The composite γ-Mg(BH4)2-LiH has a hydrogen release at T ∼380–420 °C, which indicates the formation of amorphous LiBH4 during decomposition. For the composites γ-Mg(BH4)2-NaH, formation of crystalline NaBH4 is observed by SR-PXD from T = 150–450 °C, and hydrogen release ascribed to NaBH4 is observed in MS data at T = 460–480 °C. γ-Mg(BH4)2-MgH2 composite decomposes as the individual constituents. β-Ca(BH4)2 is formed at T = 175–375 °C in the composites of γ-Mg(BH4)2-CaH2. Bragg diffraction from CaB6 at T > 370 °C is detected by SR-PXD for γ-Mg(BH4)2-CaH2 (1:0.5) but not for samples richer in CaH2. Release of diborane was not observed for any of the magnesium borohydride metal hydride composites.