The high dehydrogenation temperature of aluminum hydride (AlH3 ) has always been an obstacle to its application as a portable hydrogen source. To solve this problem, lithium nitride is introduced into the aluminum hydride system as a catalyst to optimize the dehydrogenation drastically, which reduces the initial dehydrogenation temperature from 140.0 to 66.8 °C, and provides a stable hydrogen capacity of 8.24, 6.18, and 5.75 wt.% at 100, 90, and 80 °C within 120 min by adjusting the mass fraction of lithium nitride. Approximately 8.0 wt.% hydrogen can be released within 15 min at 100 °C for the sample of 10 wt.% doping. Moderate dehydrogenation temperature slows down the inevitable self-dehydrogenation process during the ball-milling process, and the enhanced kinetics at lower temperature shows the possibility of application in the fuel cell.