High-κ and metal gate structures have been used to improve the performance of CMOS devices. By changing the materials and structures of the gate dielectric stacks, the flatband voltage (VFB) and the leakage can be changed. We used bilayers and multilayer structures composed of MgO and Al2O3 to verify their influence on the overall electrical properties. Films with an MgO bottom layer generally are found with less flatband voltage shift and lower leakage than with an Al2O3 bottom layer. Also, the frequency dispersion and the interface state density (Dit) are higher for those with MgO bottom layers. MgO films thicker than 0.5 nm effectively shields the positive charges present in the Al2O3.