LiAlH4 and CaCl2 were employed for mechano-chemical activation synthesis (MCAS) of Ca(AlH4)2 and LiCl hydride composite. After short ball milling time, their X-ray diffraction (XRD) peaks are clearly observed. After ball milling for a longer duration than 0.5 h, the CaAlH5 diffraction peaks are observed which indicates that Ca(AlH4)2 starts decomposing during ball milling into CaAlH5+Al+1.5H2. It is estimated that less than 1 wt % H2 was mechanically dehydrogenated in association with decomposition reaction. After 2.5 h of ball milling, no Ca(AlH4)2 diffraction peaks were observed on XRD patterns which suggests that Ca(AlH4)2 was decomposed. Thermal behavior of ball milled powders, which was investigated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), indicates that a certain fraction of Ca(AlH4)2 could have been disordered/amorphized during ball milling being undetectable by XRD. The apparent activation energy for the decomposition of Ca(AlH4)2 and CaAlH5 equals 135 kJ/mol and 183 kJ/mol, respectively.