The sorption properties of NaBH(4)/MH(2) (M = Mg, Ti) powder systems prepared by high-energy ball milling have been thoroughly investigated. Concerning the systems containing MgH(2), the 2:1 and 1:2 molar compositions have been studied and both lead to a multi-step desorption pathway, where the formation of MgB(2) confirms the destabilization of NaBH(4) induced by the presence of MgH(2). A noticeable kinetic enhancement is achieved for the MgH(2)-rich system (composition 1:2) if compared with the NaBH(4)-rich system (composition 2:1). Even though full re-absorption is obtained for neither of the two compositions, fast kinetics is achieved. During absorption, the unsuspected formation of the perovskite-type hydride NaMgH(3) is detected and it is showed that this ternary phase contributes to reduce the gravimetric capacity of the systems. Conversely, in the 2NaBH(4)/TiH(2) system, there is no formation of the intermetallic compound TiB(2). Furthermore, a decrease in the sorption kinetics is found in comparison with the systems based on MgH(2). (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.