From the results of this study, it can be shown that a DNA coacervate composed of DNA Ymotif nanostructures formed porous and non-porous microstructures through phase separation at the lipid monolayer interface of a W/O microdroplet (Figures and). Microscopic observations (Figure ) revealed that the cooling rate led to the formation of a porous or nonporous structure of capsular DNA coacervates. This is because competition between the VPS and gelation speeds of the DNA coacervate determines the nonequilibrium structure during the phase separation process.