In this work, poly(vinylidene fluoride) copolymer with hexafluoropropylene (PVDF-HFP) membrane-like aerogels have been generated for the first time. PVDF-HFP gels have been prepared from polymer-acetone solutions by adding various amounts of ethanol. A series of supercritical drying experiments have been performed at different pressures (from 100 to 200 bar) and temperatures (from 35 to 45 degrees C) and at various polymer concentrations (from 5 to 12 wt %). The effects of the process conditions on the membrane morphology have been evaluated, and structure-property relationships have been found. In all cases, the membranes exhibit interconnected structures with nanosized pores and high porosity, leading to reduced resistance to the gas mass transfer and high hydrophobic character of the surfaces. These membrane-like aerogels promise to form a new class of highly hydrophobic porous interfaces, potentially suitable to be used in membrane operations based, for example, on the contactor technology.