A hollow-B-ZSM-5/SS-fiber catalyst is developed through alkali leaching of the full-silica core of the silicalite-1@ B-ZSM-5 in situ structured onto a thin-felt stainless-steel fiber (20 mu m SS-fiber), which is synthesized by a seedassisted dry-gel vapor-phase transport method. As-obtained catalyst shows marked improvement in the mesoporosity- dependent diffusion (by o-xylene diffusion measurement). Boron incorporation is essential for preventing the framework dealumination during alkali leaching treatment due to the increased framework negative charges. The hollow-B-ZSM-5/SS-fiber catalyst shows remarkable stability improvement in the methanol-topropylene (MTP) reaction because of the enhanced diffusion of the nano-hollow-structure and the boron-incorporation stabilized framework aluminum. A boron-free hollow-ZSM-5/SS-fiber is also obtainable with the textural properties comparable to the hollow-B-ZSM-5/SS-fiber but shows undesired degeneration of the tetracoordinated aluminum. The preferential generation of coke in the micropores of the hollow-ZSM-5/SS-fiber causes a rapid deactivation even compared to the parent silicalite-1@ZSM-5/SS-fiber, due to the existence of extra-framework aluminum.