Asymmetric PVDF membranes were prepared by the phase inversion from casting solutions containing PVDF, NMP as solvent and 1,4-dioxane, DGDE, acetone, or GBL as additives by immersing them in water. The effects of various additives on the casting solution properties, permeation properties, and membrane structures were investigated. Low miscibility of 1,4-dioxane, DGDE and acetone with the coagulant (water) compared with NMP resulted in reducing the membrane pore size. When DGDE is used as an additive, the pore size was reduced because of its incipient sharp interface formation in the water. GBL increased membrane pore size because of its polarity compared to that of NMP. The PVDF membranes with various pore sizes could be obtained by controlling the amount of additive. The effect of mixed solvent (aqueous and non-aqueous solution) on permeation through membrane was investigated. Not only solution viscosity but surface tension affected solvent permeation.