Abstract Synthesis of lithium borohydridofluorides may pave a new way to pursue improved hydrogen storage properties of LiBH 4 as reversible hydrogen storage materials that fit the fuel cell application. The main products of the hydrogen absorption by 2LiF–MgB 2 composite are MgF 2 and LiBH 4 . In addition to them, LiBH 4− x F x compounds might be present during hydrogen absorption–desorptions and play important role on their kinetics and reversibility. First results of Near Edge X-ray Absorption Fine Structure (NEXAFS) at the B K-edge (193 eV) for LiF–MgB 2 composite with molar ratio (2:1) are presented. Obtained results indicate a formation of mixed borohydrides/borofluorides of the type of LiBH 4−x F x , thus suggesting fluorine substituting for hydrogen.