New TiO2 films have been self-assembled on solid substrate by dip-coating using TiCl4 as the titanium source and the partly fluor mated surfactant F(CF2)(8)C2H4(OC2H4)(9)OH as the liquid crystal template. By control over the dip-withdrawal speed, film thicknesses from a minimum of 43 nm were produced with rms roughnesses of 0.5-0.7 nm. The Films Were characterized by X-ray reflectivity, grazing incidence small-angle X-ray scattering, atomic force microscopy, contact angle measurements, and Raman spectroscopy. Their GI-SAXS patterns are characteristic of a 2-D hexagonal structure in which tubular rods of the fluorinated surfactant are packed hexagonally and aligned parallel to the substrate. Reflectivity and contact angle measurements of the as-prepared Film indicate that a low-density hydrophilic TiO2 surface presents to the air.