Two solid complexes of surfactants with a pendant trimethylsiiyl moiety and a cationic polyelectrolyte are prepared. These complexes form smectic A-like lamellar mesophases and low-energy surfaces (20 and 36 mN/m). The lamellar structures are characterized in detail by small-angle X-ray scattering using the interface distribution function concept. Both complexes are fabricated as highly transparent, flexible films with tensile moduli of 12 and 30 MPa and low glass transition temperatures (-10 and -56 degrees C), The application of the complexes as new coating materials is discussed.