For Li(3)AlH(6) prepared by mechanical milling method, the dissociation reaction enthalpy and activation energy are calculated to be 22.1 kJ mol(-1) H(2) and 133.7 +/- 2.7 kJ moll, respectively. The dehydrogenation performance of Li(3)AlH(6) is greatly enhanced by TiF(3) additive, especially in the kinetic behaviors. For the Li(3)AlH(6) + 10 mol% TiF(3) sample, the starting temperature of dehydrogenation is obviously decreased by 60 degrees C from that of pure Li(3)AlH(6) (190 degrees C), and 3.0 wt.% H(2) may be released within 1000 s at 120 degrees C under an initial vacuum. With the amount of TiF(3) increasing, the starting temperature decreases and the kinetics improves due to the decrease in the activation energy. The X-ray diffraction (XRD) together with thermogravimetric analysis (TGA) results show that there are three mechanochemical reactions involved during milling: i) Li(3)AlH(6) + TiF(3) -> 3 LiF + Al + Ti + 3H(2), ii) Ti + H(2) TiH(2), iii) 3 Al + Ti -> Al(3)Ti. The in-situ formed Ti species (TiH(2) and Al(3)Ti) co-catalyze the thermal dehydrogenation of Li(3)AlH(6). (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.