The growth behavior and structure of self-assembled layers of short-chain alkoxysilane of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxyl-terminated substrates were investigated using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. It was indicated that the self-assembled layers of MPS formed island structures and deposited integrally on the substrates. Further, the deposition of SnO2 thin films on the MPS-coated substrates was studied using X-ray diffraction (XRD), AFM, XPS, and the high-resolution stylus profilometers. It was proved that uniform and compact SnO2 thin films indeed formed on the self-assembled layers of short-chain MPS. The as-deposited SnO2 films were cassiterite and showed the property of semiconductors, which would have wide applications in gas sensors, solar cells, catalysts, etc. © 2004 Elsevier B.V. All rights reserved.