CeO2 thin films were deposited onto both Si (10 0) and glass substrates at a temperature between 400 and 600 degrees C using electrostatic spray-assisted vapour deposition (ESAVD). A DC voltage, ranging from 5 to 20 kV, was applied between nozzle and substrate. The surface morphology and microstructure of deposited CeO2, films were characterised using atomic force microscopy (AFM) and high-resolution scanning electron microscopy (HRSEM). The preferred orientation of the CeO2 films produced on Si (10 0) was revealed using both X-ray diffraction and pole figure measurements. Highly textured CeO2 films were formed epitaxially onto Si (100) substrates. The orientation relationships between CeO2 film and Si substrate were 001CeO(2)//001(Si) and 111CeO(2)//111(Si). However, no distinct alignment was observed in the CeO2 films deposited on glass. The results show that ESAVD is a promising deposition technique to form thin epitaxial CeO2 buffer layers onto Si (100), which is essential for the Subsequent deposition of other functional oxide films, such as high-temperature superconducting oxides. (c) 2005 Elsevier B.V. All rights reserved.