A detailed kinetic model for the bulk styrene polymerization initiated by symmetrical diperoxyester bifunctional initiators is presented. When chain termination occurs via a combination termination mechanism, six distinct polymeric species are identified in accordance with the nature of the polymer end units. It is shown that the unequal thermal decomposition characteristics of the peroxides of the bifunctional initiator system lead to the formation of polymers having considerably higher molecular weight than those obtained by the monofunctional intiator systems. It has also been found that high monomer conversion, high molecular weight, and narrow molecular weight distribution can be obtained simultaneously by using the bifunctional initiators at high reaction temperatures. This is due to the reinitiation and propagation of inactive polymers carrying undecomposed peroxides. The molecular-weight-increasing effect of the bifunctional initiator is more pronounced at high reaction temperatures. The new possibilities of increasing the monomer conversion and controlling the polymer molecular weight properties more effectively through the use of bifunctional initiators are discussed.