Amphiphilic copolymers of a methacrylic monomer (SiMA) carrying a polysiloxane side chain and an acrylic monomer (ZA) with a mixed poly(ethylene glycol) (PEG)-fluoroalkyl side chain (10-85 mol % ZA) were incorporated as the surface-active components into poly(dimethylsiloxane) (PDMS) network blends at different loadings (1 and 4 wt % with respect to PDMS). Wettability of the coating surfaces was investigated by contact angle measurements, and their surface chemical composition was determined by angle-resolved X-ray photoelectron spectroscopy. It was found that the surface segregation of the fluoroalkyl segments of the amphiphilic copolymers was responsible for the high enrichment in fluorine concentration within 10 nm of the coating surface. The PEG segments were also concentrated at the polymer-air interface. The chemical composition of the films was proven to be relatively little affected by immersion in water. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2677-2686, 2012