Ammonia borane (AB) is regarded as a highly promising candidate for chemical hydrogen-storage materials. Developing low-cost yet efficient catalysts for the dehydrogenation of AB is central to achieving hydrogen conversion. Here a heterostructure of Ni/Ni2P nanoparticles deposited on a defective carbon framework for the hydrolysis of AB is developed by elaborately controlling phosphorization conditions. The electronic structure and interfacial interaction of the ternary components are probed by synchrotron-based X-ray absorption fine structure and further simulated via density functional theory. By adjusting the content of Ni and Ni2P in the hetrostructure, the optimized hybrid exhibits catalytic performance of H2 generation from the hydrolysis of AB under ambient conditions with a turnover frequency of 68.3 mol (H2) mol-1 (Cat) min-1 and an activation energy ( Ea) of 44.99 kJ mol-1, implying its high potential as an efficient supplement for noble-metal-based catalysts in hydrogen energy applications.