Pure Ca(AlH4)2 is synthesized and its decomposition reactions are investigated in a fundamental manner. The XRD profile observed is in good agreement with the one reported by Fichtner et al. From TDS measurements, Ca(AlH4)2 appears to decompose into CaH2+2Al+3H2 in three steps. The peak temperature of the first reaction is about 470K which is higher than that for Mg(AlH4)2 (about 450K), indicating that Ca(AlH4)2 is more stable hydride than Mg(AlH4)2. In addition, the catalysis of TiCl3 is doped into Ca(AlH4)2 by ball milling under a hydrogen gas atmosphere and catalytic effects on the decomposition properties are investigated.