Two fluorinated/siloxane copolymers, 05/19 and D5/3, carrying 6 and 8 CF2 groups in the fluoroalkyl tail, respectively, were used as the surface-active components of cured poly(dimethylsiloxiine) (PDMS) blends at different loadings (0.3-5.0 wt % with respect to PDMS). The surface chemical composition was determined by angle-resolved X-ray photoelectron spectroscopy at the takeoff angles 0 of 0 degrees, 60 degrees, and 75 degrees. It was found that the fluorinated copolymer was surface-segregated, and in-depth segregation (similar to 5 run) depended upon the chemical structure of the copolymer. The Surface fluorine atomic percentage of the blends with D5/3 was up to 3 orders of magnitude higher than the theoretical value expected for ideal homogeneous samples. Moreover, small amounts of the copolymer in the blends were sufficient to saturate the outermost surface in fluorine content. The chemical composition of the surface-segregated nanostructure of the films was also proven to be affected by external environment, namely, exposure to water.