Liquid perfluorocarbons-like supercritical CO2 provide valuable reaction media that can facilitate the separation of reaction products and the recovery of catalysts. Chemistry in fluorous media requires that some of the protagonist molecules, and in particular the catalysts, be grafted with one or more perfluoroalkylated chains. These chains, due to powerful hydrophobic and lipophobic effects, tend to self-assemble and induce the formation of a variety of nanocompartmented supramolecular architectures and colloids, such as micelles, vesicles, tubules, monolayers, and emulsions, thus generating microheterogenicity in the reaction medium. Fluorinated amphiphiles are, for example, known to generate fibrous gets in fluorous, organic, and aqueous media. Phase separation, nanocompartmentation, and interface-driven parameters can thus complicate otherwise simple chemistry. Conversely, they can provide useful micro- and nanoreactors and templates. (c) 2006 Wiley Periodicals, Inc.