Cerium oxide (CeO2) thin films were deposited by e-beam PVD on various substrates, such as glass, ITO-coated glass, Si wafers and fused silica. Substrate temperature was kept constant at 125degreesC for all samples. The technological parameters of interest were oxygen partial pressure and plasma assistance during the deposition process. The basic structural properties of these films were studied by XRD, transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Composition of the samples was evaluated by X-ray photoelectron spectroscopy (XPS) and infrared transmittance (FTIR). The samples were optically characterized in the Ultraviolet-visible (UV-VIS) range (190-900 nm). The electrochromic properties of CeO2 were characterized using a lithium-based electrolyte. This paper assesses the feasibility of using pure CeO2 thin films as ion-storage layers in all-solid inorganic electrochromic devices. (C) 2003 Elsevier B.V. All rights reserved.