Complexes of a commercially available amino-functionalized polysiloxane and perfluorinated dodecanoic acid were prepared to form smooth surfaces which were highly oil- and water-repellent. The surfaces of the complexes were found to be highly enriched with CF3 groups, resulting in critical surface tensions as low as 6 mN m−1. A saturation of the surfaces with CF3 groups was reached when the degree of complexation (the ratio of acid to amino functions) was 50%. The characterization of the surfaces of the complexes was carried out using contact angle and ESCA measurements. Temperature dependent mechanical measurements of the complexes in the bulk material show that no catalyst was necessary for the cross-linking of the complexes to rubber-like materials. The complexes were proposed for the development of non-toxic anti-fouling coatings.