The atom transfer radical polymerization (ATRP) of lauryl methacrylate (LMA) with an ethyl 2-bromobutyrate/CuCl/N,N,N',N",N"-pentamethyldiethylenetri- amine initiation system was successfully carried out in toluene, and poly(lauryl methacrylate) with a low polydispersity (1.2 < weight-average molecular weight/number-average molecular weight < 1.5) was obtained. Plots of In ([M])(0)/([M]) versus time and plots of the molecular weight versus conversion showed a linear dependence, indicating a constant number of propagating species throughout the polymerization. The rate of polymerization was 0.56-order with respect to the concentration of the initiator and 1.30-order with respect to the concentration of the Cu(I) catalyst. In addition, the effect of the solvent on the polymerization was investigated, and the thermodynamic data and activation parameters for the solution ATRP of LMA were reported. (C) 2003 Wiley Periodicals, Inc.