Functional materials with a superwetting surface property have been extensively explored to achieve emulsion separation. In this paper, we report a simple and inexpensive method for fabricating superhydrophobic/superoleophilic porous materials from polymeric sponges. These microstructured porous materials, which do not contain any fluorinated compounds, maintain their superhydrophobicity and superoleophilicity after long-term organic solvent immersion and display environmental stability. These superhydrophobic porous materials can effectively separate a wide range of water-in-oil emulsions including surfactant-free and surfactant-stabilized water-in-oil emulsions with high efficiency (>99.98%) and high flux (up to 155 000 L m-2 h-1 bar-1). Meanwhile, these materials exhibited excellent pH resistance and antifouling properties. The high performance of our superhydrophobic porous materials and their efficient, low-energy, cost-effective preparation suggest that they have a great potential for practical applications.