CO2-plasma is used to introduce functional groups on the uppermost surface of an alkoxysilane self-assembled monolayer (SAM). The structural and chemical modifications of the material surface were monitored by X-ray reflectometry, atomic force microscopy, X-ray photoelectrons spectroscopy and water contact angle measurements. Optimization of the plasma parameters is performed in order to achieve a maximum functionalization and to prevent degradation of the SAM. Finally, the ability of grafting organic compounds onto the plasma modified SAMS was demonstrated by the formation of an alkoxysilane bilayer. (c) 2005 Elsevier B.V. All rights reserved.