Abstract: The kinetic features of the radical polymerization of trimethylmethacryloyloxyethylammonium methyl sulfate in micellar solutions of an oppositely charged surfactant—sodium dodecyl sulfate—are studied by NMR spectroscopy. It is shown that matrix polymerization occurs by the zip mechanism only in dilute surfactant solutions containing spherical micelles at a molar ratio of [monomer]/[surfactant] ≤ 1 and at a significant increase in the polymerization rate. An increase in surfactant concentration leads to a change in the mechanism of matrix polymerization accompanied by a decrease in the rate of polymerization, which is probably related to a change in the shape of micelles. The molecular weight of the obtained polyelectrolytes depends on the molar ratio of the components and is minimal at the [monomer]/[surfactant] equimolar ratio.