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This chapter demonstrates that metal‐catalyzed initiation of the polymerization of main chain fluorinated gaseous monomers such as vinylidene fluoride (VDF), can easily be accomplished at 0–100°C, including at rt upto 40°C, directly from a wide variety of alkyl, semifluorinated and perfluoroalkyl halides (Cl, Br, I), using a visible light, Mn₂(CO)₁₀ photomediated protocol, carried out in low pressure glass tubes, and which is especially successful in dimethyl carbonate. Fluoropolymers constitute a fundamental class of specialty materials endowed with wide morphological versatility, high thermal, chemical, aging, and weather resistance, as well as low surface energy, dielectric constant, flammability, refractive index, and moisture absorption. Typical VDF laboratory polymerizations are carried out in acetonitrile (ACN) that is a nonsolvent and a weak chain transfer agent (CTA).