RAFT-mediated self-condensing vinyl polymerization is a promising synthetic tool to create well-defined hyperbranched polymers. The functional group tolerance of RAFT, as well as the inherent ability to install readily functionalizable end groups, allow for formation of highly functionalized materials with unique properties. Due to the controlled nature of RAFT, it is possible to synthesize polymers with predetermined branching frequencies, resulting in materials with tunable properties and readily tailored macromolecular structure. This minireview gives an overview of this emerging field, emphasizing structural variety, monomer functionality, and post-polymerization modifications that have been employed to prepare previously inaccessible materials.