In this article, we describe an experimental friction study of poly(dimethyl siloxane) (PDMS) networks on metallic substrates such as gold-coated slides, and under different conditions. The friction generates a transfer of a thin layer of PDMS and a preferential orientation of the polymer chains at the interface. However, the characterization of this layer is complicated, given the small amount of matter and the contact with a metallic surface. The polarization-modulation infrared reflexion-absorption spectroscopy (PM-IRRAS), which is an excellent tool for anisotropy and orientation studies, was used to characterize the PDMS transferred layer. Our results showed an induced anisotropy due to the friction, and in which PDMS chains are lying parallel to the gold substrate surface. Our spectroscopic analyzes allowed us to imagine a scheme of PDMS transfer on the gold surface. (C) 2004 Wiley Periodicals, Inc.