The functionalization and application of nano‐objects generated using a polymerization induced self‐assembly (PISA) procedure is becoming a focus in recent years. In this contribution, using ethanol as solvent, poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA) as macro‐initiator/stabilizer, and 2‐(perfluorohexyl)ethyl methacrylate (PFHEMA) and glycidyl methacrylate (GMA) as comonomers, the initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP)‐based PISA is realized. The lower GMA content system tends to form spheres with large diameters and heavy contrast, while the lower PFHEMA content system tends to form the spheres or short worms with small diameters. However, the system with further increased GMA content results in the failed ICAR ATRP PISA procedure with the formation of precipitates by the cross‐linking reaction between pendant epoxy groups. Furthermore, using the efficient reaction between the epoxy group on GMA and thiol group on mercapto‐succinic acid agent, the carboxyl groups can be introduced into the inner cavity of the nano‐objects and used for incorporation with the Fe2+ and Fe3+ ions, and the organic–inorganic nanoparticles Fe3O4@POEOMA are finally prepared in the presence of a reductant.

The self‐assembly of copolymers containing crystallizable blocks in solution has received increasing attention in the past few years. Various strategies including crystallization‐driven self‐assembly (CDSA) and polymerization‐induced CDSA (PI‐CDSA) have been widely developed. Abundant self‐assembly morphologies are captured and advanced applications have been attempted. In this review, the synthetic strategies including the mechanisms and characteristics are highlighted and a survey on the advanced applications of crystalline nano‐assemblies is collected. This review is hoped to depict a comprehensive outline for self‐assembly of copolymers containing crystallizable blocks in recent years and to prompt the development of the self‐assembly technology in interdisciplinary fields.

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Polymerization-induced cooperative assembly (PICA), originating from polymerization-induced self-assembly, is believed to be a high-efficient method to access higher-order morphologies. Living anionic polymerization (LAP) possesses numerous advantages, such as high monomer conversion, rapid polymerization rate, and excellent controllability. We herein reported a facile strategy to prepare higher-order morphologies using a living anionic polymerization-mediated polymerizationinduced cooperative assembly (LAP PICA) process based on polyisoprene-b-polystyrene/polystyrene (PS) blends. The morphological transition ranging from spherical micelles to worms, jellyfish, vesicles, sponges, and ordered mesophases of Im3m cubosomes and p6mm hexosomes was observed and demonstrated by transmission electron microscopy, field-emission scanning electron microscopy, and small-angle X-ray scattering. Moreover, morphological distribution diagrams including factors, such as the degree of polymerization and content of the PS homopolymer, and solid contents were depicted to unveil the effect of LAP PICA on morphologies and provide guiding principles for preparing a variety of morphologies. Furthermore, a relevant morphological transition mechanism via LAP PICA was put forward.

The hydrolysis-based post-polymerization modification method was introduced into the self-assembly process and a modification-induced self-assembly (MISA) technique was presented. The diblock copolymer poly(styrene)-b-poly(tert-acrylate) (PS-b-PtBA) was employed as precursor, trifluoroacetic acid...