New fluorinated block copolymer, P(MMA/1-Hexene)-b-PVDF-b-P(MMA/1-Hexene)] was synthesized by subsequent polymerization of MMA with 1-hexene to , α,ω-diiodo-PVDF, I-PVDF-I, in the presence of radical source. The well-defined I-PVDF-I polymers were obtained by dispersion polymerization of VDF wth , α,ω-diiodoperfluorobutane(IC₄F₈I), utilizing iodine transfer polymerization(ITP). It was found that only reactive -CH₂CF₂-I chain-end structure rather than -CF₂CH₂-I could initiate the MMA/1-Hexene to form the fluorinated block copolymers.