The decomposition pathway is crucial for the applicability of LiBH 4 as a hydrogen storage material. We discuss and compare the different decomposition pathways of LiBH 4 according to the thermodynamic parameters and show the experimental ways to realize them. Two pathways, i.e. the direct decomposition into boron and the decomposition via Li 2B 12H 12, were realized under appropriate conditions, respectively. By applying a H 2 pressure of 50 bar at 873 K or 10 bar at 700 K, LiBH 4 is forced to decompose into Li 2B 12H 12. In a lower pressure range of 0.1 to 10 bar at 873 K and 800 K, the concurrence of both decomposition pathways is observed. Raman spectroscopy and 11B MAS NMR measurements confirm the formation of an intermediate Li 2B 12H 12 phase (mostly Li 2B 12H 12 adducts, such as dimers or trimers) and amorphous boron.