The book describes the use of Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization. Dithioesters are employed to conduct living radical polymerization in solution, emulsion and miniemulsion environments. The reaction mechanism is investigated in homogeneous media and supported by extensive simulations. Solution polymerizations allowed the preparation of advanced polymer architectures like e.g. block copolymers. The applications of highly active RAFT agents in heterogeneous media is complicated by stability problems. Nontheless, conditions were found that circumvented these destabilization phenomena allowing acces to designer latices of exceptionally pure block copolymers.