An elastomer was created via cross-linking a diene block of a polyisoprene-polydimethylsiloxane (PI-PDMS) block copolymer in the ordered state of hexagonal morphology, followed by the quantitative removal of the PDMS component. The elastomer material collapsed following etching of the PDMS and apparently showed no resulting nanoporosity or structure resembling the precursor morphology in contrast to similar polydiene-based nanoporous material. However, the collapsed elastomer displayed surprising properties when exposed to a solvent. In the gel state the material recovers the original nanostructure and displays liquid-filled cavities. Upon several cycles of swelling and drying the cavities open and close in a reversible fashion. When exposed to a nonsolvent, the material remains collapsed. This discriminating behavior of liquid-material interaction holds potential for the use of these materials in advanced separation or load-release systems.