<p>The article discusses the features of surface-active monomers polymerization based on n-bromoalcanol derivatives with 11, 9, 6, 3 methylene spacers between cationic and acryloyloxy groups. The polymerization products of these substances are comb-like polyelectrolytes that have proven themselves in carrying out organic reactions in water that is green and environmentally friendly solvent. Compounds with different lengths of the methylene spacer between the polymerized and polar groups of the molecule were synthesized to study the effect of micelle formation on the polymerization kinetics of surface-active monomers. Polar groups that are potentially capable to stabilize the surfactant micelle due to additional interactions (pyridinium and quinolinium cations) were introduced in the monomer molecular structure. It was found that the monomer micelles act as a kind of reservoir with surfactant molecules and practically do not participate in the propagation of polyelectrolyte during micellar polymerization. The impossibility of topological polymerization of these monomers is substantiated; as a result of micellar polymerization, a high-molecular products with a significant dispersion index (Ɖ) are formed.</p>