A kinetic study on the ring-opening polymerization CROP) of octamethylcyclotetrasiloxane (D4) in miniemulsion is presented in this work. The polymerization is initiated by dodecylbenzenesulfonic acid (DBSA) which also serves as the surfactant (inisurf). The influence of the size of monomer droplet and the concentration of DBSA on the polymerization rate were studied. Since the main place for the ROP of D4 was confirmed to be at the oil/water interface, a three-layer interface model was proposed to analyze the distribution of molecules at the interface and the effects of DBSA. A kinetic equation is then developed based on this model. In the equation, the polymerization rate (R-p) is related to the initial monomer concentration ([D4](0)), the droplet radius (r), the coverage of DBSA on monomer droplets surface (x). The polymerization rate can be predicted from the kinetic equation feeding all parameters with their experimental values. Finally, the equation gave a good accordance between the predicted polymerization rate data and the experimental results under different polymerization conditions. (C) 2010 Elsevier Ltd. All rights reserved.