For the interesting system of oppositely charged polyelectrolytes/ surfactants the driving force for their assembly is the entropic gain due to release of the small counterions and water molecules. Typically around charge equimolarity insolubility of the formed complexes is ob- served [5,7]. Such complexes, due to their ability to modify rheological properties and also their ability to incorporate active agents, are inter- esting for many applications, for instance in the field of cosmetics and pharmaceutical formulations.