Fluoropolymers are mostly insoluble in organic solvents. An attractive alternative reaction medium for the synthesis and processing of fluoropolymers is supercritical carbon dioxide, which is non-toxic, abundant, and considered to be environmentally benign. Moreover, supercritical carbon dioxide allows for the shaping of the polymers, e.g. in the preparation of well-defined polymer particles or porous materials. The material properties may be changed by the choice of pressure and temperature, which strongly affect the physicochemical properties of supercritical carbon dioxide. Supercritical carbon dioxide may be considered as a tunable reaction medium for fluoropolymer synthesis and detailed investigations into polymerization kinetics and mechanisms.