Nanocrystalline titanium dioxide/carbon composite (TiO 2 /C) was synthesized through a direct solution-phase carburization using tetrabutyl titanate (Ti(OBu) 4 ) and resol as precursors. The prepared TiO 2 /C composite was mainly in the anatase structure with an average particle size under 20 nm, which was then introduced in NaAlH 4 as a catalyst through ball milling. The desorption curves show that both nanocrystalline TiO 2 /C and TiO 2 can obviously improve the kinetics of NaAlH 4 , while NaAlH 4 with 3 mol% TiO 2 /C exhibits better cycling stability than NaAlH 4 with 3 mol%TiO 2 . The hydrogen storage capacity of NaAlH 4 with TiO 2 /C remains stable after 5th cycle, and about 94% of initial hydrogen is released, while the capacity of NaAlH 4 with TiO 2 decreases continuously during cycling, and only 88% of initial hydrogen is released after 10th cycle. Furthermore, NaAlH 4 with 3 mol%TiO 2 /C exhibits good reversibility at relatively low hydrogen pressures, and it can reload 4.16 and 1.63wt% hydrogen at 50 and 30 bar hydrogen pressures, respectively.