Nickel nanoparticles immobilized on three-dimensional nitrogen-doped graphene-based frameworks (NiNPs@3D-(N)GFs) were synthesized and examined for hydrogen generation from the hydrolytic dehydrogenation of ammonia borane. The high dispersion of NiNPs over the 3D-(N)GFs and consolidated interaction between the 3D-(N)GFs and NiNPs catalyzes the dissociation of hydrogen molecules and the subsequent migration of hydrogen atoms on the 3D-(N)GFs. Due to the unique properties of the as-prepared material such as porous structure and existence of nitrogen and nickel to have interaction with molecular hydrogen, it has high potential to be employed in hydrogen storage. The as-prepared catalyst is an ideal candidate for developing highly efficient portable hydrogen generation, which can be useful for various applications such as fuel cells, metal/air batteries, etc.