This Perspective describes the recent developments of polymerization-induced self-assembly of amphiphilic block copolymers based on controlled/living free-radical polymerization (CRP) in water. This method relies on the use of a hydrophilic living polymer precursor prepared via CRP that is extended with a hydrophobic second block in an aqueous environment. The process thus leads to amphiphilic block copolymers that self-assemble in situ into self-stabilized nano-objects in the frame of an emulsion or dispersion polymerization process. Depending on the nature and the structure of the so-formed copolymer, not only spherical particles can be achieved but also all morphologies that can be found in the phase diagram of an amphiphilic block copolymer in a selective solvent. This paper focuses mainly on aqueous emulsion or dispersion polymerization and gives an overview of the CRP techniques used, the general conditions, and the morphologies obtained.

After a brief history that positions polymerization‐induced self‐assembly (PISA) in the field of polymer chemistry, this Review will cover the fundamentals of the PISA mechanism. Furthermore, this Review will also give an overview of some of the features and limitations of RAFT‐mediated PISA in terms of the choice of the components involved, the nature of the nanoobjects that can be obtained and how the syntheses can be controlled, as well as some potential applications.