Nitrogen-doped graphene and carbon nanotubes were prepared and employed as additives to NaAlH4 to facilitate hydrogenation and dehydrogenation reactions. The decomposition behavior of carbon nanomaterial admixed NaAlH 4 was studied by constant temperature desorption, differential scanning calorimetry and in situ FT-IR experiments. Carbon nanomaterials decrease the dehydrogenation temperature of NaAlH4 and enhance the dehydrogenation kinetics by lowering the activation energy. A reversible hydrogen storage of 1.8 wt% was achieved by the nitrogen-doped carbon nanotube/nitrogen-doped graphene admixed sodium aluminum hydride. © 2013 The Royal Society of Chemistry.