Because of its apparent simplicity, diffusion of hydrogen in solids can be regarded as a general model system for diffusion. However, only rudimentary knowledge exists for the dynamics of hydrogen in complex hydrides. Insight into the specific diffusion process is given by hydrogen-deuterium exchange experiments. Thermogravimetry and Raman spectroscopy are used to measure the hydrogen-deuterium exchange during the decomposition of LiBH4. At a temperature of 523 K the self-diffusion constant of deuterium in LiBH4 is estimated to be D similar or equal to 7.10(-14) m(2) s(-1). A careful analysis of the Raman spectra shows that hydrogen is statistically exchanged by deuterium in LiBH4; i.e., the diffusing species is assumed to be the single hydrogen atom.