Films of CeO2 were deposited by atomic layer deposition (ALD) using a Ce(mmp)4 [mmp = 1-methoxy-2-methyl-2-propanolate] precursor and H2O reactant. The growth characteristics and film properties of ALD CeO2 were investigated. The ALD CeO2 process produced highly pure, stoichiometric films with polycrystalline cubic phases. Using the ALD CeO2 process, the effects of Ce doping into an HfO2 gate dielectric were systematically investigated. Regardless of Ce/(Ce + Hf) composition, all ALD CexHf1−xO2 films exhibited constant growth rates of approximately 1.3 Å/cycle, which is essentially identical to the ALD HfO2 growth rates. After high-temperature vacuum annealing at 900°C, it was verified, based on X-ray diffraction and high-resolution cross-sectional transmission electron microscopy results, that all samples with various Ce/(Ce + Hf) compositions were transformed from nanocrystalline to stabilized cubic or tetragonal HfO2 phases. In addition, the dielectric constant of the CexHf1−xO2 films significantly increased, depending on the Ce doping content. The maximum dielectric constant value was found to be nearly 39 for the Ce/(Ce + Hf) concentration of ~11%.