In this report, Ni and TiO2 are successfully embedded into porous carbon aerogel (CA) (donated as Ni-TiO2@ACA). Meanwhile, the synergistic effect of Ni, TiO2 and CA on the dehydrogenation properties of LiBH4 is systematically studied. Ni@CA, TiO2@CA and CA are also investigated for comparisons. Compared to other three materials, Ni-TiO2@CA exhibits better performance when used as a carrier to support LiBH4. More than 6.75 wt% H-2 is released from LiBH4-Ni-TiO2@CA system in nearly 120 min at 350 degrees C, exhibiting a higher dehydrogenation capacity than that of LiBH4-Ni@CA (3.15 wt %), LiBH4-TiO2@CA (5.15 wt %) and LiBH4-CA (2.05 wt %), respectively. Furthermore, the apparent energy (Ea) calculated with Kissinger method is 118.8 kJ/mol, much lower than that of pure LiBH4. Dehydrogenation performance of LiBH4-Ni-TiO2@CA may be due to the synergetic effect of destabilization of TiO2, catalysis of Ni, as well as the nanoconfinement of CA. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.