This work reports the formation of complexes between polyelectrolytes and oppositely charged surfactants solutions, and a new procedure to synthesize stable polymeric particles, where the polymerization takes place in the complex. The mixtures behavior between carboxymethylcellulose (CMe and cetyltrimethylammonium bromide (CTAB), and between chitosan (CH) and sodium dodecyl sulfate (SDS) was investigated in the diluted range at the liquid-air interface by means of surface tension, and in the bulk solution by turbidity and conductivity measurements. The synthesis of polystyrene or poly(methyl methacrylate) was carried out by emulsion polymerization in the critical aggregation concentration (cac) of the CMC/CTAB system. The hybrid particles were characterized by zeta potential, light scattering measurements and scanning electron microscopy. The colloidal stability was attributed to the presence of a hydrated CMC layer around the particles. The present procedure brings the advantage of synthesizing and stabilizing particles with functional groups on the surface in a one-step method using very small amounts of surfactant, a friendly condition for the environment.