Realizing of near room-temperature hydrogen storage in complex hydrides is the key challenge for its practical application. Here, we demonstrate a synergy strategy of confinement and metallic catalysis to enable NaAlH4 desorption close to 100 °C for the first time. As a platform for exerting the synergy effect, the Raney Ni with pore size of ~3 nm is prepared by alkali-etching and then the NaAlH4 is loaded into it via wet impregnation (denoted as NaAlH4/Raney Ni). The hydrogen desorption of NaAlH4/Raney Ni (1:4 in mass ratio) shows one step feature that starts at around 85 °C and completes at approximately 260 °C with an apparent activation energy of as low as ~20 kJ mol−1. Moreover, the dehydrogenated products of NaH + Al can readily regenerate back to NaAlH4 at 150 °C, 7 MPa H2 pressure. More importantly, the absorbed hydrogen can release again at temperature as low as 70 °C upon second dehydrogenation. These remarkable enhancements should be ascribed to both shorter diffusion routes by confining in nanoporous supports and more catalytic sites of metallic Ni, which provides an effective route to improve the hydrogen storage properties of complex hydrides by nanoporous metal supports.