α-AlH₃ is regarded as one of the most promising hydrogen storage materials due to its high hydrogen storage capacity (10.1 wt.%, 148 kg·m⁻³). However, in practical applications, the associated hydrogen release temperature remains relatively high. To effectively address this issue, hollow structured Fe@C nanorods derived from Fe-MOF are introduced as highly efficient catalyst to optimize the dehydrogenation properties of α-AlH₃. Comparatively, the initial hydrogen release temperature of α-AlH₃ + 3 wt.% Fe@C is reduced to 94.2 °C, which is significantly lower than that of pure α-AlH₃ (137.8 °C). At 100 and 120 °C, it exhibits hydrogen capacities of 5.38 wt.% and 7.47 wt.%, respectively, whereas pure α-AlH₃ only delivers hydrogen capacities of 0.24 wt.% and 5.94 wt.% under the same temperatures. The density functional theory (DFT) calculations further indicate that the existence of Fe@C catalyst can make the length of Al–H bond increase, which is more conducive to the release of hydrogen. The results show that the synergistic effect of Fe and porous carbon in Fe@C nanorods can improve the hydrogen desorption kinetics of α-AlH₃, providing a good prospect for the application of α-AlH₃ in hydrogen storage fields.