Reversible addition fragmentation chain transfer (RAFT) mediated and conventional copolymerizations at low monomer conversions have been carried out for the systems methyl methacrylate (MMA)-styrene, methyl acrylate (MA)-styrene and methyl methacrylate-butyl acrylate (BA). The polymer samples have been analyzed via H-1-NMR spectroscopy to obtain the copolymer composition and the terminal model reactivity ratios. In the RAFT mediated copolymerizations, the polymer mole fraction of the monomer with the larger reactivity ratio is increased compared to the conventional copolymerization. Simulations have been carried out using the program package PREDICI(R) to examine possible explanations for the experimental findings. The simulations demonstrate that the RAFT process itself may alter the macroradical populations and the copolymer composition by offering additional reaction pathways. Further, the rate coefficients for the initiation reaction and the pre-equilibrium play an important role in determining the copolymer composition. The rate coefficients governing the main equilibrium of the RAFT process have only a minor impact on the copolymer composition. (C) 2004 Elsevier Ltd. All rights reserved.