Abstract NaAlH 4 was melt infiltrated within a CO 2 activated carbon aerogel, which had been preloaded with TiCl 3 . Nanoconfinement was verified by Small Angle X-Ray Scattering (SAXS) and the nature of the Ti was investigated with Anomalous SAXS (ASAXS) and X-Ray Absorption Near Edge Structure (XANES) to determine its size and chemical state. The Ti is found to be in a similar state to that found in the bulk Ti-doped NaAlH 4 system where it exists as Al 1− x Ti x nanoalloys. Crystalline phases exist within the carbon aerogel pores, which are analysed by in-situ Powder X-Ray Diffraction (PXD) during hydrogen cycling. The in-situ data reveals that the hydrogen release from NaAlH 4 and its hydrogen uptake occurs through the Na 3 AlH 6 intermediate when confined at this size scale. The hydrogen capacity from the nanoconfined NaAlH 4 is found to initially be much higher in this CO 2 activated aerogel compared with previous studies into unactivated aerogels.