Polysulfone (PSf) hollow fiber membranes were prepared via the nonsolvent induced phase separation technique. The cosolvent of γ-butyrolactone (GBL) was added to the polymer solution containing a mixture of PSf and N,N-dimethylacetamide(DMAc). Water was utilized as a precipitation nonsolvent. The morphology of prepared membranes was investigated using a field emission scanning electron microscopy. The fabricated membrane showed a typical asymmetric structure such as the dense layer on the porous support layer by the addition of GBL to the polymer solution. As the concentration of GBL increased, the asymmetric porous structure was shown to be more intensified. It was thought that the added GBL played a role of enhancing the liquid-liquid phase separation of the polymer solution, since the cosolvent of GBL might change the thermodynamic solubility parameter of the doping solution. Permeation properties through the prepared hollow fiber membranes were characterized by measuring the pure water flux and the solute rejection using 0.05 μm polystyrene latex (PSL) beads. Experimental results revealed that the use of PEG as the internal coagulant enhanced the pure water flux up to 130 times compared to the use of EG while the rejection of the PSL beads decreased only 5%.