The kinetics of radical telomerization of VDF at 141°C, initiated by ditertbutylperoxide, in the presence of three chain transfer agents (CTAs), HCCl 3 , CCl 4 and CCl 3 Br, are presented. The values of the chain transfer constants were assessed as 35, 0.25 and 0.06 at 141°C for CCl 3 Br, CCl 4 and HCCl 3 , respectively. The values of the degree of polymerization (DP n ) were obtained for each CTA and were compared for the same CTA concentration. Hence, CCl 3 Br behaved as an efficient CTA towards VDF and usually afforded the monoadduct selectively, but in certain conditions the VDF diadduct can also be produced. In contrast, HCCl 3 was not so efficient since a polymeric structure was identified as the major product.