Fluoropolymers are used in many technologically demanding applications because of their balance of high-performance properties. A significant impediment to the synthesis of variants of commercially available amorphous fluoropolymers is their general insolubility in most solvents except chlorofluorocarbons (CFCs). The environmental concerns about CFCs can be circumvented by preparing these technologically important materials in supercritical fluids. The homogeneous solution polymerization of highly fluorinated acrylic monomers can be achieved in supercritical carbon dioxide by using free radical methods. In addition, detailed decomposition rates and efficiency factors were measured for azobisisobutyronitrile in supercritical carbon dioxide and were compared to those obtained with conventional liquid solvents.