Investigations into the kinetics and mechanism of dithiobenzoate‐mediated Reversible Addition–Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the rate coefficients associated with the RAFT equilibrium is discussed and methods for obtaining RAFT‐specific rate coefficients are detailed. In addition, mechanistic studies are presented, which target the elucidation of the fundamental cause of rate retarding effects. The experimental and theoretical data existing in the literature are critically evaluated and apparent discrepancies between the results of different studies into the kinetics of RAFT polymerizations are discussed. Finally, recommendations for further work are given. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5809–5831, 2006

This highlight describes recent developments in reversible addition–fragmentation transfer (RAFT) polymerization. Succinct coverage of the RAFT mechanism is supplemented by details of synthetic methodologies for making a wide range of architectures ranging from stars to combs, microgels, and blocks. In addition, RAFT reactions in different media such as emulsion and ionic liquids receive attention. Finally, a specific example of a novel material design is briefly introduced, whereas polymers prepared via RAFT are adopted for microporous/honeycomb membrane design. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 365–375, 2003