Confinement effect on the structural, electronic and thermodynamic properties of LiBH4 is investigated by density functional theory. The thermodynamically and dynamically stable confinement structure is testified to be gamma-LiBE4@C31Ti according to the adsorption energy and vibrational frequency calculations. The tridentate structure formed by [BH4](-) and Li+ in the unconfined LiBH4 changes into bidentate structure in gamma-LiBH4@C31Ti. We observe that both the occupied and unoccupied states of H 1s, B 2s, B 2p, Li 2s, and Li 2p orbitals in the partial DOSs of gamma-LiBH4@C31Ti shift to high energy level and the splits of DOS peaks occur at the states of H 1s, B 2p, and Li 2p orbitals. Different from the first-step decomposition reaction of LiBH4, the one for gamma-LiBH4@C31Ti changes into 2LiBa(4)@C31Ti -> 2LiH + 2B@C31Ti + 3H(2). Moreover, the reaction enthalpy for the first-step decomposition reaction of gamma-LiBH4@C31Ti decreases to 5.864 eV, which is smaller than that (17.204 eV) of LiBH4. According to the hydrogen removal energy calculations, we observe that the confinement effects make the removal of the first and second hydrogen atoms in gamma-LiBH4@C31Ti easy. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.