A complex catalyst for enhancing the dehydrogenation kinetics of LiAlH4 was developed by using an impregnation process to decorate TiCl3 on multiwall carbon nanotubes (MWCNTs). The effects of these composite catalysts on the dehydrogenation behavior were investigated by using thermal gravimetric analysis (TGA) and in-situ synchrotron X-ray diffraction (XRD) technique. The experimental results showed that the initial dehydrogenation temperature could be lowered by adding the appropriate amount of TiCl3-MWCNTs composite. LiAlH4 became unstable and decomposed even at room temperature when 20 wt% TiCl3 MWCNTs was added. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.