"Fluidic leakage" caused by vacuum force at the reversible sealing poly(dimethylsiloxane) (PDMS) interfaces was converted to one useable avenue, which led to formation of highly ordered surfactant microdroplets functionalized with ionic liquids (ILs). Vacuum force is the prerequisite to lead constant microsolutions to diffuse to the PDMS interfaces. Imidazolium ions of ILs rendered structural rearrangement of the surfactant aggregates and the ordered droplets formation. The anion tetrafluoroborate of ILs possessed indispensable functions in affecting the polarity of the microdroplets and was discovered to have enhanced effect on encapsulation of hydrophilic molecules in surfactant microdroplets. These interesting phenomena were characterized by various analytical methods such as confocal laser scanning microscopy, atomic force microscopy, luminescence spectroscopy and UV-vis spectroscopy.