This paper presents for the first time the extraction of chemical vapor deposition (CVD)-TiN and poly-Si work functions on atomic layer deposition (ALD)-HfO2 and high temperature SiO2 (HTO) for a wide range of EOT values. The measurements were performed on bevel oxide structures. Our results reveal that the work functions of both TiN and poly-Si gates highly depend on the underlying dielectrics especially in the case of TiN on HTO films likewise lower leakage currents depending on dielectric stacks. It is notable that when TiN is formed on the HTO film, its work function has two distinct values depending on the HTO thickness; this indicates that Ti-Si bonds strongly affect the work function variation. Both TiN on HTO and poly-Si on HfO2 show the work function shifts to about 4.3 eV, suggesting a pinning level on both structures.