Hexagonal boron nitride (h-BN) is known as an effective additive to improve the hydrogen de/absorption properties of hydrogen storage materials consisting of light elements. Herein, we report the unique hydrogen desorption properties of LiAlH 4 /h-BN composites, which were prepared by ball-milling. The desorption profiles of the composite indicated the decrease of melting temperature of LiAlH 4 , the delay of desorption kinetics in the first step, and the enhancement of the kinetics in the second step, compared with milled LiAlH 4 . Li 3 AlH 6 was also formed in the composite after desorption in the first step, suggesting h-BN would have a catalytic effect on the desorption kinetics of Li 3 AlH 6 . Finally, the role of h-BN on the desorption process of LiAlH 4 was discussed by comparison with the desorption properties of LiAlH 4 /X (X = graphite, LiCl and LiI) composites, suggesting the enhancement of Li ion mobility in the LiAlH 4 /h-BN composite.