The concept of fabricating hollow fibers with double-layer mixed-matrix materials using the same polymeric matrix has been demonstrated for gas separation. Polyethersulfone (PES)-beta zeolite/PES-Al2O3 dual-layer mixed-matrix hollow fiber membranes with enhanced separation performance have been fabricated. This study presents an innovative approach of utilizing low cost PES and Al2O3 to replace expensive polyimides as the supporting medium for dual-layer mixed-matrix hollow fibers and eliminating inter-layer de-lamination problems. The incorporations of 20 wt% beta zeolite in the outer selective layer and 60 wt% Al2O3 in the inner layer coupled with spinning at high elongational draw ratios yield membranes with an O-2/N-2 selectivity of 6.89. The presence of Al2O3 particles enables the membrane to retain its porous substructure morphology in the course of annealing above the glass transition temperature of PES. Moreover, spinning at high elongational draw ratios results in the re-distribution of Al2O3 particles towards both edges of the inner layer. Not only do the permeance and selectivity of the fibers increase, but also greater mechanical properties and lower degree of shrinkages are obtained. Therefore, the combination of PES-beta zeolite and PES-Al2O3 nanoparticles with a reasonable draw ratio may be another promising approach to produce hollow fibers with double-layer mixed-matrix materials. (C) 2008 Elsevier B.V. All rights reserved.