We have studied the effect of adding a water-soluble polymers (PEG) to the lamellar phases of the ternary system tetradecyldimethylaminoxide (C14DMAO)–hexanol–water. The results of Freeze-Fracture Electron Microscopy (FFEM) and Small Angle X-ray Scattering (SAXS) experiments show that the addition of the polymer induces the spontaneous formation of highly monodisperse multilayered vesicles above a threshold polymer concentration.