The low stability and complicated fabrication procedures seriously hindered practical applications of superhydrophobic and superoleophilic materials. Here, we present a simple method for preparing the novelly three-dimensional material based on commercially available nickel foams functionalized with electrodepositing of sub-micrometer polypyrrole (PPy) particles, followed by modification of low-surface-energy material such as fluoroalkylsilane (FAS), which can efficiently separate oils and organic solvents from water. The formation of nanostructured surface roughness of PPy onto the nickel foam by combination with FAS modification would contribute to the excellent superhydrophobic and superoleophilic performance, as is the evidence of the water CA of 155A degrees and oil CA of ca. 0A degrees for FAS-treated PPy foam. As a separating membrane, organic solvents and oils could be easily removed without obvious absorption of water, which has great potential over traditional treatment techniques and is of technological significance as a promising and efficient absorbent material for separation of organic contaminates and oils from water.