Solvent-free magnesium alanates were prepared by a mechanochemical metathesis reaction method (ball milling method) with a variation of milling time. For the purpose of comparison, magnesium alanate was also prepared by metathesis reaction method in the presence of diethyl ether. The formation of magnesium alanate (Mg(AlH4)2) and magnesium alanate-diethyl ether (Mg(AlH4)2·Et2O) adduct was confirmed by XRD measurements. In both magnesium alanates, hydrogen evolution occurred in the first step decomposition. The starting temperature for hydrogen evolution of the solvent-free magnesium alanates decreased with increasing milling time, whereas the amount of hydrogen evolution of the solvent-free magnesium alanates increased with increasing milling time. The maximum amount of hydrogen evolution of the Mg(AlH4)2·Et2O adduct was slightly larger than that of the solvent-free Mg(AlH4)2, but the starting temperature for hydrogen evolution of the Mg(AlH4)2·Et2O adduct was much higher than that of the solventfree Mg(AlH4)2. The addition of a small amount of titanium to the solvent-free Mg(AlH4)2 greatly reduced the hydrogen evolution temperature of titanium-doped Mg(AlH4)2. However, the maximum amount of hydrogen evolution of the titanium-doped Mg(AlH4)2 was smaller than that of the solvent-free Mg(AlH4)2.