Polyelectrolyte surfactant complexes made df poly(styrenesulfonate) and different alkyltrimethylammonium derivatives are "synthesized" by common precipitation in water. Redissolved in polar organic solvents, these complexes show polyelectrolyte behavior. Cast films of these complexes exhibit highly ordered mesomorphous Phases which are characterized by X-ray diffraction. Depending on alkane chain length, different layered phase modifications with long periods between 2.9 and 4.1 nm are obtained.