The hollow fiber membranes were prepared via hybrid process of the thermally induced phase separation(TIPS) and the non-solvent induced phase separation(NIPS). The spinning dope solution consisted of poly(vinylidene fluoride) (PVDF) / dibutyl phthalate (DBP) / 1-methyl-2-pyrrolidone (NMP), where DBP was used as a diluent and NMP as a solvent for PVDF. Bore fluids were tested different ratio solvent/ethanol and diluent/ethanol mixture. The membrane structure was analyzed by SEM and FT-IR to confirm phase separation mechanisms. Various structures were obtained due to the different phase separation mechanism. Membrane characterizations were performed such as water flux, pore size, rejection efficiencies and mechanical strength.