In this paper five fluorinated commercial derivatives were studied by means of ToF-SIMS. It has been found that the peaks present in the positive and negative spectra are in very good agreement with the chemical information given by the manufacturer. In addition the multivariate treatment of ToF-SIMS spectra allows a clear recognition of each compound. The width of the mass range and the intensity of these spectra however seems to be different for each compound. This might be related to the MWD and/or to the mechanism of cross-linking of some of these compounds. The complex information gathered by ToF-SIMS spectra were compared with those obtained with the static contact angle and with the water absorption by capillarity tests. (C) 2008 Elsevier B.V. All rights reserved.