Sodium aluminum hydride (NaAlH4) is a suitable medium for solid-state hydrogen storage due to its relatively high hydrogen capacity (5.6 wt.%) and moderate temperature (100~150 ℃) and pressure (≤120 bar) for reversible hydrogen release/uptake compatible with PEM fuel cells.NaAlH4 can be directly synthesized by ball milling NaH/Al co-doped with CeCl3+KH under a hydrogen pressure of 3 MPa at room temperature.