Oil spills and the emission of oily wastewater have triggered serious water pollution and environment problems. Effectively separating oil and water is a world-wide challenge and extensive efforts have been made to solve this issue. Interfacial super-wetting separation materials e.g., sponge, foams, and aerogels with high porosity tunable pore structures, are regarded as effective media to selectively remove oil and water. This review article reports the latest progress of polymeric three dimensional porous materials (3D-PMs) with super wettability to separate oil/water mixtures. The theories on developing super-wetting porous surfaces and the effects of wettability on oil/water separation have been discussed. The typical 3D porous structures (e.g., sponge, foam, and aerogel), commonly used polymers, and the most reported techniques involved in developing desired porous networks have been reviewed. The performances of 3D-PMs such as oil/water separation efficiency, elasticity, and mechanical stability are discussed. Additionally, the current challenges in the fabrication and long-term operation of super-wetting 3D-PMs in oil/water separation have also been introduced.