The dynamics and bonding of the complex hydride LiBH4 have been investigated by vibrational spectroscopy and density functional theory (DFT). The combination of infrared, Raman, and inelastic neutron-scattering (INS) spectroscopies on hydrided and deuterated samples reveals a complete picture of the dynamics of the BH4- ions as well as of the lattice. Particular emphasis is laid on a comparison between experiment and theory, revealing significant discrepancy between the two approaches for vibrations with high anharmonicity, which is related to large vibrational amplitudes. The latter is typical for librational modes in molecular crystals and pseudo-ionic crystals such as complex hydrides. The presented strategy for anharmonic frequency corrections might thus be generally applicable for this kind of materials. © 2013 Elsevier B.V.