Complexes were prepared by complexing amphiphilic dendrons (first, second, and third generations) with an oppositely charged polyelectrolyte through ionic interaction. Their chemical structure can be confirmed by nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FT-IR), and elemental analysis (EA). All of the complexes were investigated with respect to their aggregation behavior. Under the inducement of salt addition in THF, they showed interesting self-assembly behavior, forming micelles and vesicles depending on the amount of the salt. The formation of these self-assemblies has been proven by dynamic light scattering (DLS), static light scattering (SLS), and electron microscopy (EM) as well as atomic force microscopy (AFM). Dilution experiments showed that the formed vesicles have good stability against dilution as well as polyelectrolyte behavior. The formation of micelle and vesicle aggregates described in this article is probably based on the entropy effect and the shape transformation of building blocks caused by salt addition.