A superwetting three-dimensional (3D) nickel foam was prepared by a facile electrodeposition process. Wettability, surface morphology, and chemical composition were characterized with contact angle test, scanning electron microscopy, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy, respectively. According to the results, the as-prepared 3D nickel foam presented robust superhydrophobicity and superoleophilicity with good mechanical and chemical stability simultaneously. Furthermore, with the superwetting behavior, the nickel foam showed excellent oil/water separation capability with both high efficiency and lasting recyclability. Besides, the simple, low cost, and environmentally friendly fabrication process endows a scale-up of 3D nickel foam for oil/water separation and pollution disposal of leakage of organic solvents.