Atomic layer deposition of HfO2 on unmodified graphene from HfCl4 and H2O was investigated. Surface RMS roughness down to 0.5 nm was obtained for amorphous, 30 nm thick hafnia film grown at 180°C. HfO2 was also deposited in a two-step temperature process where the initial growth of about 1 nm at 170°C was continued up to 10–30 nm at 300°C. This process yielded uniform, monoclinic HfO2 films with RMS roughness of 1.7 nm for 10–12 nm thick films and 2.5 nm for 30 nm thick films. Raman spectroscopy studies revealed that the deposition process caused compressive biaxial strain in graphene, whereas no extra defects were generated. An 11 nm thick HfO2 film deposited onto bilayer graphene reduced the electron mobility by less than 10% at the Dirac point and by 30–40% far away from it.