By means of electroless copper deposition method a complex image has been fabricated in a mixture of cupric sulphate and formaldehyde, the surface and subsurface properties of which has been studied in detail by X-ray photoelectron spectroscopy (XPS) combined with sputter depth profiling technique analyzing distribution and chemical state of copper and silver. Depth profiling by XPS in conjunction with Ar⁺ sputtering shows that the catalytic activity of silver persists, catalyzing reduction of copper. The integral areas of spectra Ag3d after electroless copper deposition for 5 min at different sputtering times demonstrate that the amount of silver at the surface is greater than that in the interior. And then, the quite likely reasonable explanations are provided for the result. Additionally, the chemical shift of Ag3d XPS and deconvolution of Ag3d XPS spectrum have been also analyzed respectively at length.