Abstract: Nowadays, green chemistry is attracting more and more attention. In this paper, PVDF hollow fiber membranes were prepared by environment-friendly melt spinning and stretching method without any solvent and diluent involved in membrane preparation process. In particular, we selected perfluoroethylene propylene (FEP) as the dispersed phase and water-soluble polyethylene glycol (PEG) and calcium chloride (CaCl2) as the pore-forming agents. The influence of stretching ratio on the structure and properties of PVDF hollow fiber membranes were studied in detail based on pore size distribution, mechanical properties and oil-in-water emulsion separation performance. The results show that the dispersed phase and pore-forming agents can be uniformly dispersed in the matrix phase, the pore size distributions are relatively narrow. With the increase of the stretching ratio, the mean pore sizes and porosities of the membranes also increase. Meanwhile, the hydrophobility of the membranes decrease, but the water contact angles are all above 100°. The M-3 membrane shows a good mechanical property and separation effect for oil-in-water emulsion, of which the tensile strength can up to 19.3 MPa and the separation effects are all more than 97% at -0.02 MPa after ten cycles. The all results demonstrate that the membrane is potentially applicable in oil-water separation process.