This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) using the mechanism of reversible addition-fragmentation chain transfer (RAFT). The review covers over 700 publications from mid-2009 to early 2012, focusing on various aspects of RAFT polymerization, including reagent synthesis and properties, kinetics and mechanism, novel polymer syntheses, and applications. Significant developments have been made in novel RAFT agents, end-group transformation techniques, micro/nanoparticle production, modified surfaces, and biopolymer conjugates for therapeutic and diagnostic applications. The introduction discusses the importance of radical polymerization and the emergence of RDRP techniques, such as nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and RAFT, which allow control over the polymerization process while retaining the versatility of conventional radical polymerization. The controversy over the terms 'living' and 'controlled' in describing these processes is addressed, with IUPAC recommending that 'living' be reserved for processes without irreversible chain transfer or termination. The review highlights the key features of the RAFT mechanism, including the sequence of addition-fragmentation equilibria, and the importance of RAFT agent activity, measured by transfer coefficients. The mechanisms for retardation in RAFT polymerization, particularly in systems where it is observed, are not yet fully resolved. The section also discusses macromonomer RAFT polymerization and related processes, such as cobalt-mediated polymerization and organotellurium, organobismuthine, and organostibine-mediated polymerization. The choice of RAFT agents is discussed, emphasizing the factors influencing their effectiveness, and a summary of new and pre-existing RAFT agents and their applications is provided. The synthesis methods for RAFT agents are also outlined, including reactions of carbodithioates, dithiochloroformates, and radical-induced decomposition of bis(thioacyl) disulfides.This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) using the mechanism of reversible addition-fragmentation chain transfer (RAFT). The review covers over 700 publications from mid-2009 to early 2012, focusing on various aspects of RAFT polymerization, including reagent synthesis and properties, kinetics and mechanism, novel polymer syntheses, and applications. Significant developments have been made in novel RAFT agents, end-group transformation techniques, micro/nanoparticle production, modified surfaces, and biopolymer conjugates for therapeutic and diagnostic applications. The introduction discusses the importance of radical polymerization and the emergence of RDRP techniques, such as nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and RAFT, which allow control over the polymerization process while retaining the versatility of conventional radical polymerization. The controversy over the terms 'living' and 'controlled' in describing these processes is addressed, with IUPAC recommending that 'living' be reserved for processes without irreversible chain transfer or termination. The review highlights the key features of the RAFT mechanism, including the sequence of addition-fragmentation equilibria, and the importance of RAFT agent activity, measured by transfer coefficients. The mechanisms for retardation in RAFT polymerization, particularly in systems where it is observed, are not yet fully resolved. The section also discusses macromonomer RAFT polymerization and related processes, such as cobalt-mediated polymerization and organotellurium, organobismuthine, and organostibine-mediated polymerization. The choice of RAFT agents is discussed, emphasizing the factors influencing their effectiveness, and a summary of new and pre-existing RAFT agents and their applications is provided. The synthesis methods for RAFT agents are also outlined, including reactions of carbodithioates, dithiochloroformates, and radical-induced decomposition of bis(thioacyl) disulfides.