Au/SiO2 nanocomposites were prepared by rf-sputtering of gold on amorphous silica substrates. Deposition experiments were carried out in Ar plasmas at temperatures as low as 60 °C. Particular attention was devoted to the combined influence of the applied rf power and total pressure on the chemico-physical properties of the final nanosystems. In particular, low pressures (<0.2 mbar) and high rf powers (>20 W) resulted in a higher sputtering yield, allowing the deposition of continuous gold films on silica. Conversely, decreased sputtering yields (at higher pressures and lower powers) enabled the preparation of discontinuous Au/SiO2 nanosystems. A thorough investigation of the structure-properties relationships was attained by means of a multi-technique characterization. In particular, laser reflection interferometry (LRI) was employed for an insitu monitoring of growth processes, while glancing-incidence x-ray diffraction (GIXRD) and transmission electron microscopy (TEM) provided valuable information on the system nanostructure. Moreover, x-ray photoelectron spectroscopy (XPS), UV-Vis spectroscopy, and atomic force microscopy (AFM) were used to investigate the chemical composition, optical properties, and surface morphology, respectively. This study is dedicated to an XPS investigation of the principal core levels (Au, Si, O) of Au/SiO2 nanosystems. In particular, detailed scans for the Au 4f, Si 2s, O 1s, and C 1s regions and related data for a gold film on silica and a discontinuous Au/SiO2 specimen are presented and discussed. © 2004 American Vacuum Society.