By contrast to typical high-temperature (100-250 degrees C) telo-/polymerizations of gaseous fluorinated monomers, carried out in high-pressure metal reactors, the visible light, Mn-2(CO)(10)-photomediated initiation of vinylidene fluoride (bp = -83 degrees C) polymerization occurs readily from a variety of alkyl, semifluorinated, and perfluorinated halides at 40 degrees C, in low-pressure glass tubes and in. a variety of solvents, including water and alkyl carbonates. Perfluorinated alkyl iodide initiators also induce a controlled radical polymerization via iodine degenerative transfer (IDT). "While IDT proceeds with accumulation of the less reactive P-m-CF2-CH2-I vs the P-n-CH2-CF2-I chain ends, Mn-2(CO)(10) enables their subsequent quantitative activation toward the synthesis of well-defined poly(vinylidene fluoride) block copolymers with a variety of other monomers.