The dewatering of ethyl acetate (EA) holds a significant role in the production, and application of this important chemical material. In this study, pervaporation dehydration of EA is investigated Wing polybenzimidazole/poly(ether imide) (PBI/PEI) dual-layer hollow fiber membranes. The spinning parameters during the membrane fabrication, including the take-up speed and air gap distance, are varied and found to have a marked influence on the resultant, separation performance. Besides, doss-linking modification and post-thermal treatment are applied on-the PBI/PEI hollow fiber membranes and, their effects on the membrane performance are also investigated.,A benchmarking shows that the pervaporation performance of the dual-layer PBI/PEI hollow fiber membranes is superior to most other polymeric membranes for EA dehydration.