Ammonia borane (AB) is a potential material for chemical hydrogen storage because of its outstanding stability, high hydrogen density, and the development of highly effective hierarchical catalysts for AB hydrolysis. Herein, the hierarchical Co@Ni metal-organic framework (MOF) nanocolumn arrays (NCAs) on nickel foam (NF) were fabricated through a simple hydrothermal reaction, and the prepared catalysts were characterized using different techniques. The hierarchical Co@Ni-MOFNCA/NF acts as a catalyst for AB methanolysis for hydrogen production. The catalysts exhibited outstanding performance towards AB methanolysis with the TOF of TOF of 20.54 mol H2 mol catalyst−1 min−1. As a result, the activation energy of the Co@Ni-MOF NCA catalyst is 39.72 kJ mol−1 which is compared with some commercial solid support materials such as Al2O3 and AC. Additionally, the effects of nanocatalyst loading and temperatures were studied for the Co@Ni-MOF NCA catalyst. Further, a complete investigation proposes that the outstanding catalytic performance of the Co@Ni-MOF NCA catalyst could be attributed to the synergy between Co and Ni-MOF NCA.