Two strategies of RDRP of vinylidene fluoride (VDF) are presented. First, in contrast to the MADIX copolymerization of VDF with other comonomers (TFP, PMVE, and MAF), 1 that of VDF has been very rarely reported 2-3The synthesis of PVDF using MADIX solution polymerization was thus investigated in details More efficient protocols of solution polymerization were developed and afforded relatively well-defined PVDF.2-3 The careful polymer chain-end monitoring using MALDI-TOF as well as 1 H, 19F, and HETCOR 1H-19 F NMR nonetheless revealed that VDF reverse additions and transfer to solvent reactions affect the control of the polymerization. 2,4 Indeed, these undesired reactions are responsible for a non-negligible loss of CTA and for the accumulation of non-reactive polymer chains in the reaction medium. However, the synthesis of PVDF with high chain-end functionality was achieved, and attempts to reinitiate further chains were explored to lead to original macromonomers, block copolymers,5and dendrimers. This work is the first comprehensive studyof the MADIX solution polymerization of VDF and further trends on the limits.