Herein we review the environmentally friendly synthesis of fluorinated polymers in supercritical carbon dioxide (scCO(2)). Historically, many high-performance fluorinated materials are commercially synthesized in aqueous media using fluorinated surfactants or in non-aqueous conditions using fluorinated solvents. Our group has pioneered both the homogeneous and heterogeneous polymerization of fluorinated monomers in scCO(2). This review includes discussions on the synthesis of main-chain and side-chain fluoropolymers conducted via a chain-growth or continuous process. Specific materials consist of acrylateand styrene-based systems, poly(vinyl ether)s, tetrafluoroethylene- and vinylidenefluoride-based, as well as novel fluorinated elastomers and thermoplastics. (C) 2008 Elsevier B.V. All rights reserved.