In the present paper, we investigate the thermal and mechanical decomposition of lithium alanate (LiAlH4) milled with different metalhalides (VCl3, VBr3 and AlCl3). We observed that the thermal decomposition temperature of LiAlH4 does not depend on the metal-halide and it is decreased by 25 degrees C as compared to LiAlH4 without additives. Moreover, metal-halides enhance the decomposition of LiAlH4 and Li(3)Al(H)6. The ability of the metal-halides to decompose LiAlH4 and Li3AlH6 during milling follows the order: VCl3 > VBr3 > AlCl3 - X-ray diffraction and IR spectroscopy did not allow detecting any change on the cell volume or on Al-H bond of the doped alanate suggesting that the additives seem to do not act as substitutes into the lattice of the alanate. (C) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.