A study of the bulk free-radical polymerization of styrene in the presence of the cyclic bi- and trifunctional initiators cyclohexanone triperoxide, diethylketone triperoxide, acetone triperoxide, cyclohexanone diperoxide, and pinacolone diperoxide is reported. When these multifunctional initiators are used for styrene polymerization at high temperatures, it is possible to produce polymers with high molecular weights and narrow polydispersities at a high reaction rate. Additionally, the former initiators are used in a mixture that shows that the molecular parameters are influenced by the initiator concentration in the initiation system, in addition to the system employed. (C) 2002 John Wiley & Sons, Inc.