High‐molecular weight polymers, namely poly(N,N‐diallyl‐N‐methylammonium trifluoroacetate) and poly(N,N‐diallyl‐N‐methylamine), were prepared by radical polymerization of N,N‐diallyl‐N‐methylamine in aqueous solution in the presence of an equimolar amount of trifluoroacetic acid and by polymerization of the newly synthesized equimolecular salt N,N‐diallyl‐N‐methylammonium trifluoroacetate in gentle conditions. We have established that chain termination is controlled by the bimolecular mechanism and that degradative chain transfer to monomer transforms into effective chain transfer (see Scheme). The possibility of controlling the polymerization rate and molecular weight of polymers is demonstrated. The mechanisms of the observed phenomena are discussed.