Complexes of polyelectrolytes and surfactants are highly interesting systems and accordingly have been studied in detail so far. However, due to the large number of possible polyelectrolytes and surfactants that can be combined, basically an endless number of mixtures can be envisioned and a rich structural behavior has been observed in these systems. Pronounced synergistic effects are found when surfactants and polyelectrolytes are oppositely charged. These mixtures are used both in the solid state, as they provide an easy route for the preparation of highly structured materials [1–3] and in solution, due to the high structural variety and the often present stimuli-responsiveness of such supramolecular complexes