We have designed a unique class of surface active ionic liquids (SAILs) and utilized them to prepare IL-in-oil microemulsions as well as large unilamellar vesicles (LUVs). The IL-in-oil microemulsions were characterized by a phase behavior study, regular swelling behavior, and also by spectral shift of coumarin-480 probe molecules. The LUVs were characterized by dynamic light scattering and transmission electron microscope measurements. Our work opens up the possibility of creating a huge number of IL-in-oil microemulsions as well as LUVs simply by replacing the cation of NaAOT with a long chain cation.