In this work, we have demonstrated the design and engineering of poly(vinylidene fluoride) (PVDF)/nanosilica dual-layer hollow fibers as novel pervaporation membranes for ethanol recovery. The newly developed dual-layer hollow fiber membrane can exhibit a high separation factor of up to 29 with a sustainable high flux of 1.1 kg m(-2) h(-1), which is equivalent to the separation performance regime of inorganic membranes. Central to this performance achievement is the synergy of (1) desirable Membrane morphology, nanopore size, and high surface porosity of a thin-PVDF/nanosilica composite on a fully porous substrate accomplished by the dual-layer coextrusion technology, and (2) optimal operating downstream pressure with the aid of controlled pervaporation transport. The membrane selectivity-downstream pressure dependence of PVDF/nanosilica hybrid membranes is comprehensible via a modified pore-flow model. This study may represent a new class of membranes for ethanol-water separation.