The metal and ligand effect of a series of transition metal carbonyls in conjunction With alkyl and perfluoroalkyl halides was investigated in the initiation and control of the visible light, radical photopolymerizations of vinylidene fluoride (VDF) and respectively, in the synthesis of PVDF block copolymers. No polymerization was observed for CpMn(CO)(3), CpCo(CO)(2), Cp2Fe2(CO)(4), Cp*Cr-2(2)(CO)(4), Mo-(CO)(6), Fe(CO)(5), Cr(CO)(6), Co-2(CO)(8), Co-4(CO)(12), Fe-3(CO)(12), Ru-3(CO)(12), (PPh3)(2)Ni(CO)(2), Cp2Ti(CO)(2), and Au(CO)Cl. A free radical polymerization, and respectively an iodine degenerative transfer, controlled radical polymerization was obtained for Mn-2(CO)(10) similar to Re-2(CO)(10) >> Cp2Mo2(CO)(6) >> Cp2W2(CO)(6) with CH3(CH2)(5)-Br, CH3(CH2)(5)-I, CH3-I, CCl3-Cl, CCl3-Br, Br-(CF2)(6)-Br, and respectively with CF3(CF2)(3)-I and I-(CF2)(4,6)-I. Furthermore, while Fe(CO)(5), Cp*Cr-2(CO)(4) and Co-4(CO)(12) led to similar to CF2-I bond insertion, Re-2(CO)(10), Mn-2(CO)(10), Cp2W2(CO)(6), Cp2Mo2(CO)(6) and Cp2Fe2(CO)(4) provided quantitative radical activation of both PVDF-CH2-CF2-I and PVDF-CF2-CH2-I chain ends, and were employed in the synthesis of well-defined ABA triblock PVDF copolymers with vinyl acetate, tert-butyl acrylate, methyl methacrylate, isoprene, styrene, and acrylonitrile.