The superior light-harvesting ability of plasmonic metallic nanostructures makes them uniquely suitable for applications in the light-driven chemical transformations relevant to renewable fuels. Here we demonstrate the use of niobium nitride (NbN) nanostructures as a nonprecious plasmonic photocatalyst for the highly efficient H2 generation from the hydrolytic decomposition of ammonia borane (AB). Porous nanostructured NbN with a hierarchical flower-like nanoarchitecture was synthesized to achieve strong broadband plasmonic absorption in the visible and near-infrared (NIR) regions. The plasmonic NbN absorbers, when loaded with an optimized amount (∼2 wt %) of nanoparticulate Ni as the catalytic centers, show notably enhanced activity toward AB decomposition for H2 evolution under both visible and NIR illumination, with the reaction rates being 4.6 (>420 nm) and 2.7 (>780 nm) times higher than that of the dark reaction. Further kinetic measurements and mechanistic investigations reveal that the photocatalytic activity originates from the plasmonic hot-carrier contributions.