Oil spill and oily wastewater have now become a serious threat to the freshwater and marine environments. Porous materials with super-hydrophobicity and super-oleophilicity are good candidates for the oil adsorption and oil/water separation. Here, flexible hybrid nanofibrous membrane (FHNM) containing SiO2'/polyvinylidene fluoride (PVDF) microspheres was prepared by simultaneous electrospinning and electrospraying. The obtained FHNM combined the flexibility of the nanofiber mat and super-hydrophobicity of the microspheres, which could not be achieved by either only electrospinning or only electrospraying. It was found that when the weight ratio between the SiO2 and PVDF reached a critical value, the SiO2 nanoparticles were present on the PVDF microsphere surface, significantly improving the surface roughness and hence the contact angle of the FHNM. Compared with the pure electrospun PVDF nanofiber mat, most of the FHNMs have a higher oil adsorption capacity. The FHNM could separate the oil with water quickly under the gravity and displayed a high efficiency and good reusability for the oil/water separation. More importantly, the FHNM could not only separate the oil with the pure water but also the corrosive solution including the salt, acid and alkali solution. (C) 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.