Batch anionic ring-opening polymerization of octamethylcyclotetrasiloxane in emulsion using nonionic and cationic emulsifiers was studied. The concentration of emulsifiers was set above their critical micelle concentration. Effects of emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/initiator (KOH) ratio on the kinetics, average particle size and distribution and on the average molecular weight and distribution were investigated and discussed. At the beginning of the polymerization, empty micelles, active micelles (polymer particles) and monomer droplets co-exist in emulsion. The transport of monomer from monomer droplets toward empty micelles was confirmed by monomer droplets and empty micelles disappearance and by formation of smaller particles. The transport of monomer from monomer droplets toward polymer particles was not confirmed, since the average polymer particle size did not increase during polymerization. It was proposed, that at lower conversions, monomer diffuses from polymer particle interior to particle surface, while at higher conversions, the monomer diffuses from larger to smaller polymer particles. Emulsifier concentration, nonionic/cationic emulsifier ratio and cationic emulsifier/KOH ratio have an evident effect on the kinetics and on the average molecular weight, thus demonstrating that cationic emulsifier participates to the initiation reaction. (C) 2011 Elsevier Ltd. All rights reserved.