Dehydrogenation behavior of LiAlH4 (lithium alanate) admixed with multi-walled carbon nanotubes (MWCNTs) was investigated by using high-pressure thermal gravimetric analysis (HPTGA) and in-situ synchrotron X-ray diffraction (XRD) technique. HPTGA results indicated that MWCNTs play a catalytic role in the dehydrogenation of LiAlH4, subsequently decreasing the dehydrogenation temperature and improving the desorption kinetics. With the proper amount of MWCNT, the initial dehydrogenation temperature of LiAlH4 decreased by approximately 60 degrees C. Furthermore, in-situ synchrotron XRD analysis confirmed the dehydrogenation reaction products and paths of LiAlH4, with and without MWCNT addition. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.