Anti-fouling copper hydroxide nanowires (CHNs)-graphene oxide (GO) nanocomposites membrane was fabricated by a vacuum-assisted filtration self-assembly process. CHNs were covered on the surface and inserted into the interlayers of the GO nanosheets to form the rough surface and nanostructure channels. The membrane with water contact angles (CAs) of 53° and oil CAs of 155° exhibited superior stability, hydrophilicity, underwater superoleophobicity and ultralow oil adhesion, and hence it could separate the oil-water emulsion with a high efficiency of >99%. This membrane showed the combined advantages of high oil rejection rate and ultralow membrane fouling, making it promising for practical oil-water emulsion separation applications.