: Designing novel polyfluoropolymer architectures is attractive for the development of new applications, such as advanced coatings, purification membranes, or materials for energy. Nevertheless, controlling the radical polymerization of fluoroalkenes is very challenging due to the high reactivity of the propagating fluorinated macroradicals. This study aims at exploring the controlled copolymerization of perfluorohexylethylene (PFHE) and vinyl acetate (VAc) in order to prepare a range of well-defined statistical poly(PFHE-stat-VAc) copolymers with different compositions. Cobalt-mediated radical polymerization demonstrated to be active at 40 °C starting from an alkylcobalt(III) initiator, and copolymers with a fluorinated monomer content as high as ca. 80 wt % were successfully prepared. Reactivity ratios were determined to be rVAc = 0.18 and rPFHE = 0 at 40 °C and emphasized a clear tendency for alternation. Unprecedented PFHE/VAc containing block copolymers were also prepared via a single-step approach or through sequential copolymerizations. Finally, hydrolysis of the pendant ester groups of these copolymers led to the corresponding fluorinated copolymers bearing vinyl alcohol (VOH). A preliminary solution behavior study, carried out by dynamic light scattering and transmission electron microscopy on block copolymers composed of PFHE and VAc or VOH units, evidenced a marked amphiphilicity of the copolymer composed of an extremely hydrophobic PFHE block associated with a highly hydrophilic PVOH segment.