Spontaneous, single-walled, equilibrium vesicles can be prepared from aqueous mixtures of simple, commercially available, single-tailed cationic and anionic surfactants. Vesicle size, surface charge, or permeability can be readily adjusted by varying the ratio of anionic to cationic surfactant. Vesicle formation apparently results from the production of anion-cation surfactant pairs that then act as double-tailed zwitterionic surfactants. These vesicles are quite stable in comparison to conventional vesicles prepared by mechanical disruption of insoluble liquid crystalline dispersions.