Formation of polyelectrolyte-surfactant complexes (PESCs) in polymerization process of corresponding amphiphilic monomer is a promising way of pure stoichiometric PESC obtained in salt-free systems. Polymerization of micelle-forming monomer dodecylammonium 2-acrylamido-2-methylpropanesulfonate (DDA-AMPS) in different media was studied by means of ¹H-NMR and conductance measurements. Kinetics of polymerization in direct micelles, inverted micelles, and homogeneous solution was considered in terms of classical solution polymerization and microemulsion polymerization. Reaction orders on monomer and initiator were measured in water and dioxane. The rate of polymerization is strongly dependent on monomer micelle existence, being considerably higher in micellar solution than in homogeneous one. [Figure not available: see fulltext.]