Pd/Ag films were electrolessly deposited onto p-silicon (100)-activated seed layers of Ag and Pd, respectively, in the solution of 0.005 mol l AgNO ∈+∈0.005 mol l PdCl ∈+∈4.5 mol l NH ∈+∈0.16 mol l Na EDTA+0.1 mol l NH NH (pH 10.5) at room temperature. The morphology and composition of the films were studied comparatively by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Cathodic polarization curves for hydrogen evolution were recorded in 0.5-mol l H SO without illumination, in which the obtained films served as working electrodes. The experimental results show that the film obtained on the Ag seed layer was rather a pure Ag film and not a Pd/Ag film, and the Ag deposition rate on Pd sites was much faster than that on Ag sites. © Springer-Verlag 2007.