Metal-complex hydrides Li3AlH6 and V-doped Li3AlH6 nanoparticles were synthesized by solid reactions of LiH and LiAlH4 in the absence and in the presence Of VCl3, respectively. X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller sorption, thermogravinietry and differential thermal analysis have been used to investigate the phase composition, microstructure and surface properties. Not only the nanocrystalline Li3AlH6, but also the coexisting catalyst with "valence-transfer" state can influence the dehydrogenation kinetics. The extension of the catalytic mechanism is attractive for reversible hydrogen storage of the alanate system.