Fluorination treatment has been performed on polysiloxane membranes using a plasma glow discharge of a gases mixture CF4 and argon (plasma enhanced chemical vapor deposition). Atomic force microscopy, XPS analyses and contact angle measurements have been undertaken to explain the surface transformation and behavior, which strongly depend on the morphology, the composition and the hydrophilic/hydrophobic character of the plasma-polymerized initial membranes. Main result is that fluorination, which leads to hydrophobic membranes, has a more relevant effect on amorphous silica-like membranes than on polymer-like ones, according to their chemical composition whereas the plasma surface reaction induces a substantial microstructural modification of the polymer-like membrane, i.e. the grains and aggregates size and distribution. (C) 2002 Elsevier Science B.V. All rights reserved.