The frequent occurrence of oil spill accidents and the illegal discharge of industrial oily sewage not only cause a waste of natural resources, but also seriously damage our ecological environment. Intelligent oil/water separation materials are feature with the cyclically reversible wettability between hydrophilicity and hydrophobicity, which can flexibly deal with various oil/water mixtures and shows an excellent oil-water separation ability. In this paper, the phenomenon of surface wettability and mechanism of switching wettability are introduced, and the research progress of intelligent oil/water separation materials is reviewed according to the different external stimuli, such as pH, temperature, light, gas and etc. Finally, the main problems and challenges in this field are presented, and its future development direction is prospected.