Poly(vinylidene fluoride)-containing block copolymers are difficult to prepare and still very rare in spite of their potential use in high added value applications. This communication describes in detail the synthesis of unprecedented poly(ethyl vinyl ether)-block-poly(vinylidene fluoride) (PEVE-b-PVDF) block copolymers (BCP) via the sequential combination of cationic RAFT polymerization of vinyl ethers and radical RAFT polymerization of vinylidene fluoride (VDF). Dithiocarbamate chain transfer agents were found to efficiently control the radical RAFT polymerization of VDF and to be suitable for the preparation of PEVE-b-PVDF BCP. These new block copolymers composed of incompatible polymer segments may find applications owing to their phase segregation and self-assembly behavior.