AbstractAmphiphilic block copolymers of poly(ethylene glycol) (PEG) and poly(vinylidene fluoride) (PVDF) were successfully synthesized by growing poly(vinylidene fluoride) on PEG‐chain transfer agent (PEG‐macro‐CTA) using reversible addition–fragmentation chain transfer (RAFT) polymerization. MeO‐PEG‐XA, and XA‐PEG‐XA macro‐CTAs (XA refers to the xanthate moiety), synthesized by esterification of MeO‐PEG‐OH (20,000 g mol−1) and HO‐PEG‐OH (20,000 g mol−1) with 2‐bromopropionyl bromide followed by reaction with potassium ethyl xanthate, were used to synthesize MeO‐PEG‐b‐PVDF and PVDF‐b‐PEG‐b‐PVDF, respectively. The synthesized macro‐CTAs and block copolymers were characterized by NMR (1H, 13C and 19F), FTIR, and SEC. Furthermore, the PVDF/PEG block copolymer formation was proved by 1H DOSY NMR. The thermal properties were determined by TGA and DSC. The crystallinity and electroactive phases were revealed by XRD and FTIR. The size and shape of self‐assembled block copolymers in DMF/water mixtures were determined by DLS, TEM and critical micelle concentration with fluorescence spectroscopy. The influence of molecular weight and PVDF content on the properties of copolymers is discussed.