The synthesis of yolk/shell spheres including a movable magnetic core, a poly(ionic liquid)s-derived porous carbon shell, and nickel nanoparticles confined within the porous shell is reported. The as-prepared carbon shell is graphitic and porous, as proven by X-ray diffraction, Brunauer–Emmett–Teller equation, and transmission electron microscopy characterizations. The ensuing catalyst has been employed for the tandem dehydrogenation of sodium borohydride and hydrogenation of several nitro/nitrile compounds in aqueous media, which resulted in high yields with a very low amount of the catalyst.