A fluorinated polyelectrolyte-surfactant complex is shown to form highly ordered lamellar structures in the bulk material and in spin-cast films with a long period of 3.75 nm consisting of alternating fluorinated and polymer-rich layers. The smectic B-like structure was found to be stable up to temperatures of 185 degreesC. The wetting behavior of complex films with thicknesses in the range of 5.7-370 nm were investigated by using axis-symmetric drop shape analysis of contact angle measurements. Surface energies were calculated using the equation derived by Neumann and Li (ca. 11 mN/m), the Zisman critical surface tension (7 mN/m!, and the Girifalco-Good-Fowkes dispersive surface energy (10 mN/m). The surface energies were found to be independent of the thickness of the films. By use of X-ray reflectivity it was found that up to 100 double layers were oriented macroscopically on silicon wafers when prepared by the spin-coat technique.