The major challenge of complex hydride for hydrogen storage is to release hydrogen at a moderate temperature with rapid kinetics. This paper reports a new composite system (NaBH(4)/ZnF(2)) to generate hydrogen at a low temperature below 100 degrees C. The NaBH(4) and ZnF(2) mixture was prepared by a mechanical milling in a 2:1 M ratio. Dehydrogenation of the mixture during a heating process shows that the initial dehydrogenation temperature was below 100 degrees C with favorable kinetics. The structural analysis confirmed the formation of NaBF(4) and Zn in the reaction products. The study concerning the reaction mechanism reveals that ZnF(2) plays a role of reagent rather than catalyst. The produced intermediate of NaZnF(3), however, affects the decomposition of the emitted B(2)H(6). This work suggests that the extension of the decomposition mechanism of NaBH(4)/ZnF(2) composite system would favor the development of new catalysts for complex hydride systems. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.