Nanocrystalline titanium dioxide loaded carbon spheres (Ti-CSs) with 10wt% TiO 2 were synthesized through an easy one-step method using phenolic resols, titania nanoparticles and Pluronic F127 as organic carbon sources, inorganic precursors and surfactant, respectively. The results show that the as-prepared Ti-CSs composite is spherical shape with a diameter ranging from 0.3 to 2 μm, and rutile TiO 2 nanoparticles are distributed on the surface of the carbon spheres. Then the kinetics of NaAlH 4 was improved through depositing it on the surface of as-prepared Ti-CSs by melt infiltration. The results show that NaAlH 4 with Ti-CSs exhibits better hydrogen desorption kinetics than TiF 3 or nanocrystalline TiO 2 catalysted-NaAlH 4 , and it starts to release hydrogen at about 40 °C and releases about 25% of the hydrogen content during heating to 60 °C. The results from SEM and XPS show that hydrogen storage properties of NaAlH 4 were considerably improved due to the formation of special structure during melt infiltration and the nanocrystalline TiO 2 and/or amorphous phase Ti–Al clusters near the subsurface sites, which succeed in combining catalyst addition (TiO 2 nanoparticles) and nanoconfinement to improve the kinetics of NaAlH 4 .