The polymerization kinetics for the preparation of poly(p-divinylbenzene (p-DVB)) via a miniemulsion process was studied by the gravimetric analysis and the transmission electron microscopy (TEM) analysis. The influence of the variation of both initiator concentration and polymerization temperature on the polymerization rate was investigated and also the activation energy of p-divinylbenzene was estimated. The evolution of polymer particles was observed by the electronmicrographs and the relatively large size of polymer particles without the formation of coagulum was obtained in the miniemulsion polymerization process. (c) 2008 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.