Three-dimensional separation materials with robust physical/chemical stability have great demand for effective and continuous separation of immiscible oil/water mixtures and water-in-oil emulsions, resulting from chemical leakages and discharge of industrial oily wastewaters. Herein, a superelastic polystyrene-based porous material with superhydrophobicity/superoleophilicity was designed and prepared by high internal phase emulsion polymerization to meet the aforementioned requirements. A flexible and hydrophobic aminopropyl terminated polydimethylsiloxane (NH 2 -PDMS-NH 2 ) segment was introduced into the rigid styrene-divinylbenzene copolymer through 1, 4-conjugate addition reaction with trimethylolpropane triacrylate. The addition of NH 2 -PDMS- NH 2 simultaneously improved the mechanical and hydrophobic properties of the porous material (the water contact angle from 141.2 degrees to 152.2 degrees ). The material exhibited outstanding reversible compressibility (80% strain, even in liquid N 2 environments) and superhydrophobic stability, even after being repeatedly compressed 100 times, water contact angle still remained above 150 degrees . Meanwhile, the as -prepared material had outstanding hydrophobic stability in corrosive solutions (strong acidic, alkaline, high -salty, and even strong polar solvent), presence of mechanical interference, strong UV radiations, and high/low temperature environments. More importantly, the material could continuously and efficiently separate immiscible oil/water mixture and water -inoil emulsions under the above conditions, showing huge potential for the large-scale remediation of complex oily wastewaters.