The interfacial reactions and electrical characteristics of stack structures of La 2 O 3 and Al 2 O 3 were investigated as a function of the annealing temperature. In the case of Al 2 O 3 /La 2 O 3 /Si (ALO structure), the La 2 O 3 in contact with the Si substrate was readily transformed into La-silicate by the diffusion of Si atoms, while in the case of La 2 O 3 /Al 2 O 3 /Si (LAO structure), interfacial reactions between the Al 2 O 3 layer and the Si substrate were suppressed. After an annealing treatment at 700 °C, the Al 2 O 3 in the ALO structure can play an effective role in blocking the hydration of La 2 O 3 , resulting in an unchanged interfacial layer. However, the Al 2 O 3 layer in the LAO structure was unable to suppress the diffusion of Si atoms into the La 2 O 3 film. When the annealing temperature reached 900 °C, both structures showed a similar depth distribution with a high content of Si atoms diffused into the films. The change in the elemental distributions via the diffusion and reaction of Si atoms affected the electrical characteristics at the interface between ALO/LAO structure and Si substrate, specifically the trap charge density ( D it ) and band gap ( E g ) values.