At present, new high-k dielectric materials are being intensively investigated to replace the silicon dioxide as gate dielectric for the next generation of electronic devices. Several candidate materials (such as ZrO2, HfO2, Al2O3) and deposition processes are currently under investigation. Because the layer thickness which is required in the next generations of devices is of the order of few nanometers, a precise determination and control of layer thickness will be mandatory. Although spectroscopic ellipsometry (SE) is well established non-contact, non-destructive and precise technique for determining thickness and optical properties of thin films, it becomes more difficult to obtain this information unambiguously and simultaneously for ultra-thin films with traditional SE alone because of possible high correlations between film structure and optical properties. The grazing x-ray reflectometry (XRR) is a complementary nondestructive optical technique and can be used to unambiguously determine ultra thin film thickness accurately. Combined with ellipsometry technique together, it will provide a promising way to characterize high-k gate dielectrics including thickness, roughness, interfacial layers and material composition information etc. In this paper, the principles for both SE and XRR will be briefly reviewed and limitation of each technique will be discussed. Following the high-k gate dielectric exploration and development, examples of using the combined SE/XRR techniques will be presented.