Developing an efficient oily wastewater treatment method has become an urgent problem due to the increasing severe situation of oil pollution. Here, the s-kaolin particles modified PAN composite membrane with super-hydrophobicity and superoleophilicity was successful fabricated through electrospinning. The composite membrane exhibited good oil adsorption capacity to different kinds of oil and organic solvent, and the maximum absorption capacity achieve 37.2 times of its own weight. Moreover, the composite membrane can efficient separate immiscible oil/water mixtures with excellent separation efficiency (above 95 %) and high separation flux (1960.1 L h(-1)m(-2)). Due to tolerance to most solvents of the PAN, the composite membrane possess good stability after adsorbed oil and separated oil and water mixtures (more than 10 cycles). Furthermore, the composite membrane shows considerable separation efficiency toward different kinds of water-in-oil emulsion under impressed pressure. The excellent separation ability, high porosity and good recyclability of the composite membranes allowed their potential application in practical oily wastewater treatment in environmental protection.