CeO2/Gd2O3 multilayers were prepared on Si (100), quartz and inconel-783 substrates by pulsed laser deposition technique at an oxygen partial pressure of 2 Pa and substrate temperatures of 300 and 873 K. The layer thickness of CeO2 was varied from 5 to 30 nm, whereas Gd2O3 layer thickness was kept constant (∼10 nm). The phase and crystallite size of the films were characterized by X-ray diffraction (XRD), X-ray reflectivity (XRR), Raman spectroscopy, atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) techniques. The layer thicknesses, measured by XRR as well as from HRTEM micrographs were in good agreement with each other. The CeO2/Gd2O3 multilayers show transmittance of ∼70%. Nanoindentation measurements indicated that the hardness values of the multilayers were higher than that of single layers of CeO2 and Gd2O3 thin films.