It is well-established that X-ray reflectivity (XR) is an invaluable tool to investigate the structure of thin films. Indeed, this technique provides under correct analysis, the electron density profile of thin films in the direction perpendicular to the substrate. For thin films that exhibit lateral ordering at the nanometer scale, grazing incidence small angle X-ray scattering (GISAXS) ideally complements the XR technique to measure the scattering in off-specular directions. As typical examples, XR and GISAXS data of mesoporous silica thin films and porous materials are presented. The analysis of the XR curve allows to determine the porosity of the film. We also show that the combination of X-ray and visible optical reflection provides information about the index of refraction of thin films. Finally we report how capillary condensation of water can be monitored by XR and GISAXS. (c) 2006 Elsevier B.V. All rights reserved.