Oil removal or oil/water separation from the industrial waste water especially under harsh environment such as acid and alkali solutions have now been becoming an urgent task for human being. Here, flexible nanofibrous membrane with super-hydrophobicity/super-oleophilicity was prepared through a facile one-step solution-immersion approach, i.e., the poly(vinylidene fluoride) nanofiber mat modified with methyltrichlorosilane (MTS). The nanostructured polysiloxane with different morphologies including the ultrathin cylindrical wires and particles, were present on the nanofiber surface after MTS hydrolysis and subsequent condensation, which significantly enhanced the surface roughness and hence the hydrophobicity of the membrane. The influence of MTS concentration in the n-hexane solution and the hydrolysis time of MTS on the morphology of polysiloxane decorated nanofiber and hence the super-hydrophobicity was investigated in detail. The super-hydrophobic nanofibrous membrane could repel hot water and corrosive solutions, and the contact angle maintained around 150 degrees with a pH ranging from 1 to 13. It was found that the oil/water separation with a high flux and efficiency was achieved by using the nanofibrous membrane that could not only separate the oil with the pure water and hot water but also the corrosive solution including the salt, acid and alkali solution. The organic/inorganic hybrid nanofibrous membrane may have find its potential applications in oil/water separation under a harsh environment.