The experimental system that enables thin film deposition by chemical vapor deposition combined with magnetron sputtering and sample surface characterization by photoelectron spectroscopy (PES), without breaking the vacuum between the deposition and the characterization stage, is described. The particular goal of this work was study of the surface arrangement of embedded metallic nanoclusters of 1B group (Au, Ag, and Cu) in amorphous hydrogenated carbon (a‐C:H). From the range of applied material characterization tools, we present here the results of several PES‐based experiments used to reveal cluster properties at the surface: as‐deposited sample PES measurements, off‐normal take‐off angle XPS, andin situin‐depth XPS profiling by Ar+ion etching. Clear distinction in all PES results of the samples deposited on the grounded substrates from those deposited on −150 V dc biased ones is obtained, revealing that keeping the substrate grounded during deposition results in topmost metallic clusters covered with a very thin layer ofa‐C:H, while applying negative bias voltage to the substrate results in partially bald clusters on the surface. © 2004 American Institute of Physics