In this study, novel stellate poly(vinylidene fluoride) (PVDF)/polyethersulfone (PES) microsphere-nanofiber membrane with special wettability was successfully prepared via electrospinning technique. The structure properties are confirmed with SEM, FTIR, TG-DTG and EDS, which indicated that the PES/PVDF composite nanofibers was successfully fabricated. Moreover, the applications of the PES/PVDF membranes as a filter membrane for oil/water separation, we could find that the obtained PES/PVDF membranes showed excellent performance in separation of oil (transform oil)/water mixture. (C) 2017 Elsevier B.V. All rights reserved.