Novel hydrophobic Hyflon® AD /PVDF membranes were developed and investigated for n-butanol dehydration via pervaporation. The coating protocols for thin defect-free Hyflon® AD selective layer on the PVDF support was optimized. Water and n-butanol transport was measured, analyzing the effect of operating conditions. The water flux through the newly developed membranes was higher than 150 g/m2.h with 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.