The hydrogen sorption properties of calcium borohydricle (Ca(BH4)(2)) catalyzed with a small amount of TiF3, TiCl3, NbF5 or NbCl5 are investigated using thermal analyses and X-ray diffraction. NbF5 exhibits the best performance among all the catalysts: it causes a decrease in the hydrogen desorption temperature which leads to hydrogen absorption at practical temperature and pressure conditions. The hydrogen content of Ca(BH4)(2) with NbF5 reaches about 5.0wt.% after hydrogen absorption at 693 K for 24 h under 90 bar of hydrogen. The main dehydrogenation product of Ca(BH4)(2) with NbF5 is a CaH2-xFx solid solution with a CaF2 (Cl) structure, while pure Ca(BH4)(2) produces CaH2 after hydrogen desorption. (C) 2008 Elsevier B.V. All rights reserved.