The hydrogen storage material of Ti-doped Na alanate has been studied by using both experimental and theoretical Ti K-edge X-ray absorption near edge structure (XANES) analysis. The results suggest the existence of small TiAlxTiy nanoclusters with not more than 13−35 atoms in NaAlH4 after the intercalation of Ti and hydrogenation−dehydrogenation cycling. The results rule out the possibility of the formation of both TiTi4Al8 nanoparticles and TiAlx nanoparticles having a TiAl3 type of local structure.