Polymerizable water-insoluble surface-active macromers (SAMs), namely ⊍,ω-divinylpolydimethylsiloxane (DVPDMS), ⊍,ω-dipropylmethacrylatepolydimethylsiloxane (DPMPDMS) and ⊍,ω-pair(vinylbenzyl)polydimethylsiloxane (PVBPDMS), were synthesized and characterized using NMR. The colloidal-chemical properties of the synthesized compounds were studied in comparison with non-polymerizable polydimethylsiloxane. Using DVPDMS, DPMPDMS and PVBPDMS as copolymerizable emulsifiers, polystyrene and poly(methyl methacrylate) suspensions with large particles, narrow particle size distribution and with the absence of the residual surfactant in the waste water were obtained. It is shown that in the presence of DPMPDMS it is possible to obtain polymer suspensions with an average particle diameter of 1.6 ∼m. The proposed mechanism of the effects of the SAMs on the polymerization is based on the copolymerization with the main monomers in the monomer-polymer particle interphases which results in stabilization of the particle protective layers from early stages of the reaction.