A novel polyvinylidene fluoride-co-hexafluoropropyle (PVDF-HFP)/graphene (GE) tubular nanofiber membrane (TNM) for application in continuous oil/water separation was firstly fabricated in this study. The obtained PVDF-HFP/GE TNMs showed outstanding mechanical properties due to the reinforcement of polyester braided tube. In addition, the effect of GE concentrations on membrane structure and performance was investigated by field-emission scanning electron microscopy, hydrophobicity, pore size and its distribution, porosity and liquid entrance pressure. The results showed that, the prepared TNMs had ideal membrane structure and performance with moderate addition of GE. When the GE concentration was 0.03 wt%, the obtained TNMs exhibited a superior selective wettability and could achieve separating surfactant- stabilized water-in-oil emulsion with a remarkable separation rate and separation efficiency.