The functional properties of liquid crystal (LC) thin films are correlated to their structure and microstructure. Moreover, not only phase and order of LC are important parameters influencing these properties, but also thickness, density, and roughness of the film. In this paper a study of multilayer systems LC/ITO/glass based on GIXRD (Glancing Incidence X-Ray Diffraction) and XRR (X-Ray Reflectivity) experiments is proposed. It is shown that the nominal thickness of the ITO layers may be wrong. The determination of this parameter and, generally, the structural characterization of the display can be performed by XRR and GIXRD. Moreover, also very thin layer as SiOx obliquely evaporated for the LC alignment, can be precisely determined.