Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied controlled/living radical polymerization methods that has been used to prepare well-defined nanostructured polymeric materials. This review, with more 650 references illustrates the range of well-defined functional nanomaterials that can be accessed using RAFT chemistry. The detailed syntheses of macromolecules with predetermined molecular weights, designed molecular weight distributions, controlled topology, composition and functionality are presented. RAFT polymerization has been exploited to prepare complex molecular architectures, such as stars, blocks and gradient copolymers. The self-assembly of RAFT-polymer architectures has yielded complex nanomaterials or in combination with other nanostructures has generated hybrid multifunctional nanomaterials, such as polymer-functionalized nanotubes, graphenes, and inorganic nanoparticles. Finally nanostructured surfaces have been described using the self-organization of polymer films or by the utilization of polymer brushes. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 551-595, 2011