Attempts were made to spin hollow-fiber membranes from poly(Vinylidene fluoride) (PVDF) material by the dry-wet phase inversion method. Hollow fibers so prepared were characterized for various parameters and by electron microscopic techniques. Membranes were also tested for the separation of water/1-propanol mixtures in vapor phase. It was found that the hollow fibers were water selective despite the fact that PVDF material is hydrophobic. Intrinsically organic selective property of PVDF material was proved by coating a porous polyetherimide membrane with a PVDF layer, which resulted in enhancement of I-propanol permeation while suppressing the permeation of water.