Pulsed laser deposition was used to grow thin (1–100 nm) magnesium oxide films directly on graphite and epitaxial graphene on SiC(0001). The authors observe very smooth (typical rms roughness of ∼0.4 nm) film morphologies that are nearly independent of film thickness and conformal to the substrate for films grown on room temperature substrates. Surface roughness is less than 1 nm for thicknesses up to 100 nm and is independent of oxygen background pressure during growth. X-ray diffraction shows no evidence of crystallinity for films grown on room temperature substrates but shows ⟨100⟩ texture for films grown on heated substrates that also have very rough surface morphologies. X-ray photoelectron spectroscopy shows hydroxylation of films due to air exposure that can only be partially removed by annealing, indicating the presence of atomic defects in the films.