Poly(etherimide) hollow fiber membranes for the oxygen enrichment were prepared by dry-wet phase inversion processes from spinning solution containing NMP and an alcohols as a nonsolvent-additive. The alcohols used in this study include four alcohols(methanol, ethanol, propanol, buthanol) and diethylene glycol. The effect of the alcohols as nonsolvent-addi-tive on the spinning solution properties; permeation fluxes of pure O2 , N2 ; and structures of the PEI hollow fiber membrane were investigated. The PEI hollow fiber membrane with an outer diameter of about 450 mm and inner diameter of about 150 mm were prepared. The PEI hollow fiber membrane prepared from NMP/MeOH solvent systems exhibited the best gas separation charac-teristics. After silicon coating, these hollow fiber exhibited approximately a oxygen permeance 0.5 GPU with a 5.7 selectivity to nitrogen. Through SEM microphotograph we also got a finger-like(C1-C4 alcohols), sponge-like(diethylene glycol) substructures.