The separation of oil and water is a worldwide challenge due to the ever-increasing amount of oily industrial wastewater and polluted oceanic waters, as well as the increasing frequency of oil spill accidents. As the leader of advanced fibrous materials, electrospun nanofibers combine the properties of tunable wettability, large surface area, high porosity, fine flexibility, and ease of scalable synthesis, have a great potential for the separation of oily wastewater. Herein, we successfully fabricated superhydrophilicsuperoleophobic membranes by depositing doped polyaniline(PANI) on the surface of electrospun polyamide-6(PA6) nanofibers mat by in situ polymerization method. The coated mat was applied in the eparation of oil/water mixtures and non surfactant oil in water emulsion with the designed separation setup under the different pressures (from 0.1-1 bar). The newly designed PA6/PANI membranes can effectively separate oilwater mixtures and oil in water emulsion with a high separation efficiency (> 95%) and good water flux(100 L.m2.h-1) thus possess great potential for oilwater separation.