Improving the dehydrogenation behavior of aluminum hydride (AlH₃) by introducing additives provides a promising avenue in portable hydrogen source applications. However, the challenge remains in the development of highly active additives that facilitate hydrogen storage in composites while maintaining high capacity with a relatively small amount of additive. This work presents the successful synthesis of TiN nanoparticles by nitriding reaction using TiO₂ as the precursor. The onset dehydrogenation temperature of AlH₃ could be remarkably reduced to 52.9 °C on account of the catalytic effect of TiN nanoparticles. Furthermore, the composite exhibits a close approximation to the realistic capacity of pure aluminum hydride, with a maximum capacity of 9.9 wt.%. The notable decrease in the apparent dehydrogenation activation energy of AlH₃ from 130.86 to 86.69 kJ·mol⁻¹ after the incorporation of TiN substantiates the pivotal role of multivalent titanium and nitrogen.