Electrostatic self-assembly can be used to form supramolecular vesicles in aqueous solution. Vesicles consist of cationic G8 poly(amidoamine) dendrimers and the trivalent sulfonate dye Ar27. No classical amphiphiles are present but the interplay of electrostatics, pi-pi interaction and geometric factors influences the structure formation. Labeled guest molecules, both small molecules and peptides, can be included inside these vesicles and vesicles imaged by fluorescence techniques. The structure was studied by dynamic and static light scattering, small-angle neutron scattering, confocal laser scanning microscopy, and fluorescence correlation spectroscopy. The study indicates the prospect of constructing functional nanoobjects by the self-assembly of charged molecules in aqueous solution.