The self‐assembly of amphiphilic diblock copolymers in block selective solvents is well documented in the scientific literature. It gives rise to micelles in which the insoluble blocks form a core, which is surrounded by a corona that contains the soluble blocks. Another method to trigger micellization consists in introducing additional non‐covalent interactions such as electrostatic interactions or hydrogen bonding in an initially soluble block copolymer. The non‐covalent complexes that result from these interactions should be insoluble in order to induce micellization. Such insoluble complexes can be generated by mixing, in a non‐selective solvent for all the individual blocks, two block copolymers or a block copolymer and a homopolymer, that contain mutually interacting blocks. This mixing process may, therefore, lead to insoluble non‐covalent complexes, which further aggregate into micellar cores stabilized by the uncomplexed blocks. Such a strategy has been successfully implemented in both aqueous and non‐aqueous solvents to create interesting stimuli‐responsive systems, mainly using ionic interactions and hydrogen bonding. This feature article will summarize these approaches.
