A mass of oil-water mixture is generated in oil exploitation, and a large amount of oil-water wastewater is produced in our daily life. If these oily wastewaters are not treated effectively, direct discharge would cause serious damage to the natural ecology. How to deal with these oil-water mixtures is a critical issue of environmental protection and sustainable development. Due to the different composition and dispersion form of oily wastewater, and the harsh condition in the actual treatment process, the separation method should be selected to satisfy the separation requirements. Membrane separation is a common oil-water separation method. The separation principle is based on the different affinity of oil and water to the solid film surface. However, due to the diversity of separation environments and the limited mechanical properties of membrane materials, membrane separation has encountered kinds of challenges in industrial applications, especially for the high concentration of oil in water. In this work, nickel foam with good mechanical properties is used as filtration materials, and nano-structures are constructed on its surface to enhance the roughness of substrate surface and the underwater oil-repellency, so as to improve the oil-water separation performance. By electrochemical deposition method, copper particles are deposited on the surface of nickel foam. The surface structure and properties of the separation film are characterized by X-ray diffractometer, surface roughness tester and contact angle tester. The oil-water separation property to different kinds of oil and the stability of the prepared separation film are tested. The results show that the membrane has a high separation efficiency for different kinds of oil and good cycling separation performance, and the separation efficiency is more than 95% after ten cycles. This study shows the effectiveness of surface engineering in the development of efficient membrane for oil-water separation, and expands the applications of electrodeposition approach to surface modification.