Poly(vinylidene fluoride) (PVDF) is a very important fluoropolymer which possesses remarkable physicochemicalproperties such as high thermal and chemical resistances as well as ferroelectricity, for example.To date, only iodine transfer polymerization and RAFT polymerization have enabled the preparation ofwell-defined PVDF and of some PVDF-based block copolymers (BCPs). However, these reversible deactivationradical polymerization techniques suffer from undesired reactions which impair the synthesis ofa wide range of PVDF-containing BCPs. Here, unprecedented poly(vinylidene fluoride)-block-poly(2-(dimethylamino)ethylmethacrylate)(PVDF-b-PDMAEMA) BCPs were prepared by CuAAC click coupling ofazide-functionalized PVDF synthesized by RAFT polymerization and alkyne-functionalized PDMAEMAsynthesized by ATRP. This strategy was quite efficient and afforded three relatively well-defined BCPs(PVDF40-b-PDMAEMA23, PVDF40-b-PDMAEMA69, PVDF40-b-PDMAEMA162, Đ < 1.55). These amphiphilicBCPs were self-assembled in water at pH 2, 8 (native pH) and 10. The morphologies obtained were mainlypolydisperse (20–500 nm), roughly spherical aggregates. However, at pH 8, PVDF40-b-PDMAEMA69 alsoformed micrometer-long rigid cylindrical micelles. These morphologies are likely the first examples ofPVDF-containing BCP nanostructures produced by crystallization-driven self-assembly