A NiO–Ni foam composite carrier was prepared by the hydrothermal method. Ruthenium metal was supported on the NiO–Ni foam by electroplating, obtaining a highly active bush-like Ru/NiO–Ni foam catalyst. To investigate the effect of NiO on the structure and performance of the catalyst, a Ru/Ni foam catalyst was prepared as a reference. The structures of the carrier and both catalysts were characterized by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy, and the performances of both catalysts were evaluated in alcoholytic hydrogen production from sodium borohydride. On the carrier with the NiO-treated surface, the active component Ru developed a three-dimensional bush-like structure that enhanced the catalytic activity. Indeed, the hydrogen production from alcoholysis of sodium borohydride was three times higher on the Ru/NiO–Ni foam catalyst than on the Ru/Ni foam catalyst, and the highest rate exceeded 6 L/g/min. The repeated-use stability of the Ru/NiO–Ni catalyst (10 times) also exceeded that of Ru/Ni foam (8 times). However, as both catalysts used the same active component (i.e., Ru), their activation energies were almost identical.