The spontaneous formation of vesicles in the aqueous of cationic surfactant phosphate(PTA) and anionic surfactant sodium dodecyl sulfate (SDS) at certain mixing ratios have obtained1.The addition of urea or NaI will expand the range of spontaneous vesicle formation. The fact is demonstrated by negative-staining transmission electron microscope(TEM) and dynamic light scattering(DLS) methods. The phenomenon especially in the part of urea is reported by us at first.Mechanism of urea/NaI-induced vesicles formation is discussed from the viewpoint of the molecular geometry packing parameter f, conformation and interaction.