Controlled free radical polymerizations of methyl methacrylate and styrene in bulk by 1,1-diphenylethene (DPE) were demonstrated in a two-step process, preheating treatment of initiators followed by a living polymerization of monomers. Over the course of polymerization, continuous growing of polymers with unimodal molecular weight distribution and a relatively small polydispersity index (around 1.5 even in the range of Mn similar to 10(5) g/mol) on GPC diagrams was observed. In our previous study, the DPE controlled radical polymerization with constant molecular weight throughout the polymerization was caused by the intrinsically low reactivation rate constant (k(2)) of DPE capped dormant chains. To raise the reaction temperature in order to increase k(2), a continuous molecular weight growing but broader or bimodal molecular weight distribution was obtained if the living polymerization was conducted in a one-step process. In this work, a two-step polymerization process was proposed. In the first step, the initiator 2,2'-azobisisobutyronitrile (AIBN), control agent DPE, and small amount of monomer were mixed and heated for a specific time period. Then a living polymerization of monomers was conducted in the second step of polymerization. This two-step new approach had minimized the imperfections of the DPE system; thus the polymerization showed better living characters and revealed its enhanced control abilities. (C) 2010 Elsevier Ltd. All rights reserved.