By phase inversion process, the polyvinylidene fluoride (PVDF) with polyvinyl chloride (PVC) blend membrane was prepared. In which, as pore-forming agents, the polyethylene glycol (PEG), poly(vinylpyrrolidone) (PVP) and lithium chloride (LiCl) was separately added into PVDF/PVC casting solution. The effect of each pore-forming agent on the kinetics of membrane formation and properties of PVDF/PVC blend membrane were investigated respectively. Using the capillary flow porometry, the microstructure and morphology of PVDF/PVC blend membrane were quantitatively characterized. The results show that by respectively adding PEG, PVP or LiCl, it emphasizes the rate of solvent diffusion from PVDF/PVC solution during the phase inversion or membrane formation, and the porosity of membrane gets increasing. The pure water flux of PVDF/PVC blend membrane achieves enhancement obviously. At the same time, the rejection is decreased in a certain degree. Comparison with PEG or LiCl, PVP has more effect on the membrane pore-forming action. The microstructure analysis indicates that based on the same formulation, by selecting PEG or LiCl as pore-forming agent, formatted PVDF/PVC blend membranes achieve equivalent mean pore size. However, there is a little larger mean pore size distributed in the membrane by using PVP instead of PEG or LiCl. The application of purifying ε-polylysine (ε-PL) by using the PVDF/PVC blend membrane with PVP, the results reveal that the protein removal rate can be around 62.33% and the filterable and permeated ε-PL kept at 70.79% yield.