A NiB binary catalyst with a unique mulberry-like nanoparticle morphology has been prepared by one-step electrodeposition. The NiB-0.2 catalyst exhibits excellent catalytic activity, selectivity, and stability for the borohydride oxidation reaction. Moreover, a direct borohydride fuel cell using the NiB-0.2 catalyst anode can deliver a peak power density of 453 mW cm-2 and open-circuit voltage of 1.96 V at 343 K. The improved performances are due to the introduction of B. This study may inspire the development of efficient noble-metal-free anode catalysts for DBFCs.