We have studied applicability of reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) method to radical cyclopolymerization of protonated diallylammonium monomer, namely diallylammonium trifluoroacetate (DAATFA), occurring with efficient chain transfer to monomer reaction. The latter drives to a significant extent polymerization, noticeably setting molecular weight, MW, of polymers and their polydispersity (polydispersity index (PDI) = 2.8–3.0). For the first time, upon DAATFA polymerization in presence of RAFT ethylxanthogenacetic acid (xanthate) in aqueous solutions at 70 °C, the side chain transfer reaction was inhibited and control of the polydispersity was achieved, the PDI = 1.2–1.3. The structural characteristic of poly(diallylammonium trifluoroacetate) (PDAATFA) polymers was analyzed via ¹H and ¹³C NMR and IFS FTIR (ATR) spectroscopy. It was proved that the structure of polymers obtained by RAFT polymerization fully corresponds to the polymers PDAATFA containing cationic pyrrolidinium links and trifluoroacetate-counterions. At the optimal xanthate concentrations, the main products are polymers with the end dithiocarbonate group, i.e. macro-RAFT PDAATFA. Static/dynamic light scattering, viscometry and ultracentrifugation were used for polymers characterization. Molecular weight was determined by two independent methods: static light scattering (M_w) and hydrodynamic parameters analysis (M_Dη). The PDI M_w/M_n was calculated on the basis of Fujita approach, using the determined distributions of sedimentation coefficients. The experimental number average molecular weights, M_n, grow with polymerization time, 6700 g mol⁻¹ < M_n < 10500 g mol⁻¹, but did not correspond to the theoretical one. The rate of polymerization mediated by xanthate was shown to increase approximately twice in comparison to free-radical process that distinguishes DAATFA RAFT polymerization from other processes mediated by RAFT agent.