Sodium alanate (NaAlH4) is a prospective H2 storage material for stationary and mobile applications, as NaAlH4 contains 7.4 wt% of H2, and it is possible to do multiple H2 release and accumulation cycles. Nanoconfinement is a potential solution to enhance the H2 release properties of NaAlH4. To optimize the supporting material and the synthesis method used for the nanoconfinement of NaAlH4, a better understanding of the influence of nanoconfinement on the H2 release processes is necessary. Thus, the H2 release from bulk, purely nanoconfined, and intermediate NaAlH4 is measured at different temperature ramp rates, and the characteristic parameters for each hydrogen release process are determined. Activation energies for each process are determined using the Kissinger method, and the effect of nanoconfinement on the activation energies is analysed. The impact of nanoconfinement on the H2 release processes from NaAlH4 and the limitations of each process in case of bulk and nanoconfined NaAlH4 are presented and discussed. Nanoconfinement of NaAlH4 decreases activation energies of the initial reversible H2 release steps to between 30 and 45 kJ mol−1 and increased the activation energy of the last irreversible H2 release step to over 210 kJ mol−1.