AbstractSpectroscopic Ellipsometry (SE) and Grazing X‐ray Reflectance (GXR) techniques are applied for different insulating films to determine precisely the thickness and optical indices of the layers. Antireflective coatings for microlithography in the DUV range are first analyzed. In the infrared range the layers are transparent and one can take into account the optical index of the layers by a simple dispersion law. Thicknesses obtained by this method are checked by the GXR technique. Extraction of the optical indices from UV to IR is made very accurately taking into account different SE measurements at various incident angles simultaneously. Amorphous carbon thin films are also analyzed in the same way. The main difference is that the layer is absorbant in the entire wavelength range. In this case, a first characterization by the GXR technique is essential to extract the thickness of the layer. Then the optical indices of the layer can be extracted very accurately by SE.