The application of hexagonal boron nitride materials in the field of catalysis has gradually attracted increasing attention. Herein we demonstrate the application of porous boron nitride nanofibers as a promising carrier for developing highly efficient catalysts for the catalytic hydrogenation of ammonia borane. Porous boron nitride nanofibers with high specific areas are utilized as a novel carrier to support and immobilize CuCo binary metal nanoparticles with average diameters below 10 nm. The prepared composite catalyst exhibits excellent catalytic activity on hydrogen production by ammonia borane hydrolysis. The hydrogen generation rate of Cu0.4Co0.6/boron nitride catalyst (with a particle loading weight of 15.6 wt%) is 3387.1 mL min(-1).g(-1), with a total turnover frequency value of 8.42 mol H-2.(mol cat)(-1).min(-1) and a activation energy of 21.8 kJ mol(-1). Theory study indicates that the synergistic effect of CuCo binary metals, as well as the strong interaction between boron nitride carrier and CuCo metal, leading to the enhanced catalytic activities of the catalyst. This study demonstrates that porous boron nitride has prospective application potentials in the field of catalytic hydrogen production of ammonia borane.