Seeking of novel materials with special wettability is highly demanded for efficient separation of emulsified mixtures. In this study, carbonized melamine foam modified with cobalt hydroxide nanosheets was fabricated by a two-step route consisting of thermal pyrolysis and controlled chemical precipitation. The developed material exhibited a superamphiphilicity in air, and a controlled superoleophobic or superhydrophobic performance in various liquid conditions. By utilizing these properties, the composite foam was used as a bi-functional material to separate various oil-water emulsions. The results demonstrated that the developed material, solely using gravity without external stimulus, had the capability to separate not only the surfactant-stabilized oil-in-water emulsions with a high separation flux, but also the water-in-oil ones with remarkable oil purity. The facile method for the material preparation, high separation merit and excellent anti-fouling property of material provided a new candidate for the separation of emulsion systems.