In this work the application of XPS technique to the study of five fluorinated compounds deposited on actual calcarenite samples is presented. It has been found that the composition derived from the high-resolution XPS spectra together with the results of the C 1s fitting, allow us to derive a surface chemical formula for each of the studied compounds. These formula are in good agreement with those reported in the manufacturer data sheets if one hypothesise an arrangement of these molecules on the surface of the calcarenite stone that take into account the content of the different hydrophobic groups. In addition, the thickness of the deposited film has been calculated on the basis of the Ca and C content as well as an estimation of the coverage degree has been done. The results of this XPS study has been compared with that obtained by means of the static contact angle test. (C) 2007 Elsevier B. V. All rights reserved.