Counterion polymerization of (DDA-AMPS) is suggested as a new route for preparation of organosoluble polyelectrolyte-surfactant complexes. The polymerization was performed in water and water-dioxane mixed solvent systems. Micellar properties of the monomer were studied. High molecular weight samples of the polymer complex (above 106) were obtained in solvent systems with high and small (0–5%) content of water. The complexes were studied in organic solutions by viscometry, isothermal diffusion, and by AFM on mica and as free films.