Stacked gate dielectrics composed of CeO2 and La2O3 were fabricated on Si substrates and their structures and electrical properties were investigated. Two types of stacked structures were compared: CeO2 grown on La2O3 (La2O3/CeO2) and La2O3 grown on CeO2 (CeO2/La2O3). The La2O3 and CeO2 layers were formed by atomic layer deposition (ALD) and chemical vapor deposition (CVD), respectively. The La2O3/CeO2 structure showed a larger equivalent oxide thickness (EOT) than the CeO2/La2O3 structure due to the silicate formation of the CeO2 layer in contact with Si. Metal–oxide–semiconductor field-effect transistors (MOSFETs) and capacitors constructed with the La2O3/CeO2 structure showed threshold and flat-band voltages close to the ideal ones. Effective channel mobilities for the MOSFETs were compared among three structures: single-layer La2O3, La2O3/CeO2, and CeO2/La2O3. EOT scaling was achieved without degrading the mobility of the CeO2/La2O3 structure, which reproduced previous results for the same structure formed by the electron-beam evaporation technique. The gate-leakage characteristics for the CVD/ALD samples were also investigated.