The effect of multi-walled carbon nanotubes (MWCNTs) addition on the dehydrogenation behavior of NaAlH4 (sodium alanate) is investigated using high-pressure thermal gravimetric analysis (HPTGA) and in-situ synchrotron X-ray diffraction (in-situ synchrotron XRD) technique. The HPTGA results show that the addition of MWCNTs facilitates dehydrogenation of NaAlH4 by lowering the first-step dehydrogenation temperature to 80 degrees C. In-situ synchrotron XRD analysis demonstrates that the dehydrogenation pathway can be modified by the addition of MWCNTs which resulting in an enhanced hydrogen desorption rate and reduced desorption temperature. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.