Superhydrophobic composite nanofibrous membranes(PP) were prepared from polycaprolactone (PCL)/polystyrene (PS) through solution blow spinning with an airbrush for oil adsorption. PP membranes were characterized by fourier transform infrared spectroscopy, scanning electron microscopy, water contact angle, X‐ray Photoelectron Spectroscopy, X‐ray diffractometer, and thermogravimetric analysis instrument. The effects of mass ratio of PCL and PS on the morphology, porosity, density, cyrstallinity, thermal stability, and oil adsorption ability were investigated. PP membranes had higher density than PCL and PS, while better hydrophobicity. The saturation adsorption capacity of PP to peanut oil, motor oil, and diesel oil is 16.89 g/g, 20.33 g/g, and 12.17 g/g, respectively. After 6 cycles of reutilization, the adsorption capacity to peanut oil, motor oil, and diesel oil remained at 6.16, 7.46, and 5.33 g/g, respectively, higher than that of pure PCL membrane.The water/oil adsorption selectivity of PP was about 7:100. PP had higher oil adsorption capacities and better water/oil adsorption selectivity than the commercial oil absorbent polypropylene. PP membrane could be prepared and used in situ to separate oil from oil/water mixture. POLYM. ENG. SCI., 59:E171–E181, 2019. © 2018 Society of Plastics Engineers