Sulfur-free hydrogen production is significant for sustainable energy such as fuel cell to avoid poisoning catalysts. The hollow fiber membrane is proposed as sulfur trapper for the hydrocarbon fuels. Hollow fiber membranes with polyimide (PI) matrix and adsorptive zeolites fillers are fabricated by dry-wet spinning with subsequent imidization process. By detailed investigation of FT-IR, thermal degradation cures, morphology and sulfur trapping performance, the molecular structure, thermostability and adsorption channels of membranes have been analyzed. The hollow fiber membranes have abundant pores, and the zeolites particles are incorporated in the three-dimension polymer matrix. The inlet fuel can be desulfurized to below 0.1 mg L-1, which means that the outlet fuel can be used as sulfur-free hydrogen source for fuel cell applications. Excellent sustainability of the system with hollow fiber configuration show attractive on-board application potential. Copyright (c) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.