Over the last ten years, the use of self-assembly processes for the formation of new materials has attracted increasing interest. Such processes are promising in mimicking nature to form e.g. lamellar nanostructures in bulk materials and also at surfaces. The complexes of diazosulfonate polymers and fluorinated surfactants are typical examples of such materials. They form thermally stable lamellar structures in the solid state with repeat units of 3 to 4 nm and are classified as mesomorphous polyelectrolyte fluorinated amphiphile complexes (PEFA). Ionic layers that contain the diazo functions alternate with nonionic layers (containing the perfluoroalkyl chains). Thin and ultra-thin films can easily be produced from diazosulfonate polymer surfactant complexes by common film-forming methods such as spray and spin coating techniques. The surfaces of the PEFA films display interesting wetting properties such as tunable surface energies. The lowest critical surface energies, for example, are about 8 mN/m. The surfaces switch reversibly to higher surface energies (about 30 mN/m) when in contact with water.