The hydrogen dynamics in solid and in liquid LiBH4 was studied by means of incoherent quasielastic neutron scattering. Rotational jump diffusion of the BH4 - subunits on the picosecond scale was observed in solid LiBH4. The characteristic time constant is significantly shortened when the system transforms from the low-temperature phase to the high-temperature phase at 383 K. In the molten phase of LiBH 4 above 553 K, translational diffusion of the BH4 - units is found. The measured diffusion coefficients are in the 10-5cm2/s range at temperatures around 700 K, which is in the same order of magnitude as the self-diffusion of liquid lithium or the diffusion of ions in molten alkali halides. The temperature dependence of the diffusion coefficient shows an Arrhenius behavior, with an activation energy of Ea = 88 meV and a prefactor of D0 = 3.1 ×10 -4cm2/s. © 2010 American Chemical Society.