In this study, we use vacuum UV spectroscopic ellipsometry (VUVSE) to characterize new high dielectric materials. Indeed, all the candidates for high k dielectrics become strongly absorbent when the wavelength is reduced down to 140nm. So, the correlation between thickness and refractive index is reduced in the VUV range and much more precise structural information can be deduced. HfO2, Al2O3and mixed HfAlOxlayers have been studied with and without thin SiO2oxide at the interface. X‐ray reflectometry (XRR) has been used to measure precisely the layer thickness and roughness. The two techniques are included in the same automated metrology system dedicated to 300mm technology which is also presented. We show in particular that VUVSE can detect the crystalline character of the layers and their composition can be measured in addition to the layer thickness. Results are compared to those obtained by transmission electron microscopy (TEM), x‐ray fluorescence analysis (XRF) and x‐ray photoemission (XPS). © 2003 American Institute of Physics