A mechanochemical process for the synthesis of alane (AlH3) starting from lithium hydride (LiH) and aluminium chloride (AlCl3) at room temperature and the underlying reaction pathway have been studied. In contrast to a conventional process using the same two reactants dissolved in diethyl ether, our approach enables a solvent-free synthesis, thereby directly leading to adduct-free alane. The method described here is quick and efficient, resulting in the quantitative conversion of all aluminium in the starting mixture to alane. Both the intermediate compounds formed during the reaction and the final products have been characterized by powder X-ray diffraction, solid-state27Al NMR spectroscopy, and temperature programmed desorption analysis of the as-milled mixtures. We show that excess LiH in the starting mixture (with an optimal ratio of 9LiH : 1AlCl3) is essential for the formation and stability of Al–H bonds, initially in the form of alanates and, eventually, as alane. Further processing of this mixture, gradually adding AlCl3to reach the ideal 3LiH : 1AlCl3stoichiometry, appears to restrict the local accumulation of AlCl3during the ball-milling process, thereby preventing the formation of unstable intermediates that decompose to metallic Al and molecular hydrogen. We also demonstrate that under the milling conditions used, a moderate hydrogen pressure ofca.300 bar is required to suppress competing reactions that lead to the formation of metallic Al at room temperature. The identification of the reaction intermediates at each stage of the synthesis provides significant insight into the mechanism of this solid-state reaction, which may potentially afford a more rational approach toward the production of AlH3in a simple solvent-free process.