A reverse-barrier technique is used to enable the treatment of electrospun poly(vinylidene fluoride) nanofibrous membranes with supercritical carbon dioxide. The treatment induces the formation of nanopores and extended-chain beta crystallites of small lateral dimensions in the nanofibers. It also creates interfiber junctions, resulting in a remarkable improvement in mechanical properties of the membranes. The treated membranes are able to retain their shape very well after loading with an ionic liquid (IL). The ionic conductivity of the IL-loaded membrane is very close to that of the neat IL.