Novel hydrophobic Hyflon AD/poly(vinylidene fluoride) (PVDF) membranes were developed and investigated for n-butanol dehydration via pervaporation. The coating protocols for a thin defect-free Hyflon AD selective layer on the PVDF support were optimized. Water and n-butanol transport was measured, analyzing the effect of the operating conditions. The water flux through the newly developed membranes was higher than 150 g/m2·h, with the selectivity for water higher than 99 wt %. The focus was on the use of Hyflon AD as the selective layer for n-butanol dehydration. The membrane application can be extended to other solvents, supporting an effective and simple method for dehydration with hydrophobic membranes.