This article provides a critical review of the properties, synthesis, and applications of dithiocarbamates Z ' Z '' NC(=S)SR as mediators in reversible addition-fragmentation chain transfer (RAFT) polymerization. These are among the most versatile RAFT agents. Through choice of substituents on nitrogen (Z ', Z ''), the polymerization of most monomer types can be controlled to provide living characteristics (i.e., low dispersities, high end-group fidelity, and access to complex architectures). These include the more activated monomers (MAMs; e.g., styrenes and acrylates) and the less activated monomers (LAMs; e.g., vinyl esters and vinylamides). Dithiocarbamates with balanced activity (e.g., 1H-pyrazole-1-carbodithioates) or switchable RAFT agents [e.g., a N-methyl-N-(4-pyridinyl)dithiocarbamate] allow control MAMs and LAMs with a single RAFT agent and provide a pathway to low-dispersity poly(MAM)-block-poly(LAM). (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 216-227