The phase behavior of an aqueous catanionic surfactant system, composed of a long-chain imidazolium ionic liquid 1-dodecyl-3-methylimidazolium bromide (C(12)mimBr) and sodium dodecyl sulfate (SDS), is described. The phase diagram of the catanionic system was determined by electrical conductivity measurements and the formation of vesicles in a birefringent L-alpha phase characterized by transmission electron microscopy (TEM) and freeze-fracture transmission electron microscopy (FF-TEM). Rheological measurements were used to characterize the macroscopic properties of the birefringent L-alpha phase. Both electrostatic and hydrophobic interactions contribute to the vesicle formation in the catanionic system. Compared to the DTAB/SDS aqueous solution, differences between the imidazolium and trimethylammonium headgroups geometric packing and charge density induce the different phase behavior in each system. Silica hollow spheres, with diameters 30-60 nm and a wall thickness of 8-10 nm, were prepared by using the vesicles as the templates. The hollow silica spheres were characterized by TEM, scanning electron microscopy (SEM), and nitrogen adsorption-desorption. The results suggest additional application for ionic liquid based vesicles to be used as templates for the synthesis of hollow inorganic materials.