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The widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non‐covalent interactions, still presents tremendous challenges. Herein, we propose a co‐assembly strategy to fabricate hierarchical chiral mesostructures by combining a liquid crystalline block copolymer (LC‐BCP) with a small molecular amphiphile containing chiral alanine or phenylalanine as a linker. Through a classic solvent‐exchange process, chiral amphiphiles embedded within LC‐BCP finely regulate the LC ordering effect and facilitate transfer and amplification of asymmetry. Consequently, various co‐assembled structures with significant hierarchical chirality features are obtained through synergetic effects. Remarkably, subtle alterations to the side groups of amino acids in the amphiphiles effectively adjust the hierarchical morphology transition. Moreover, the covalent bonding sequence of amino acids in the amphiphiles emerges as a critical factor governing the formation of hierarchical nanofibers and multilayered vesicles exhibiting a superhelical sense. [ABSTRACT FROM AUTHOR]

Functional hierarchy is prevalent in biological systems owing to natural evolution. Efforts to replicate these structures in artificial materials have gained traction in materials science. Although artificial hierarchical structures are fabricated at different scales based on site‐specific interactions using ABC‐type block copolymers (BCPs), the fabrication of such hierarchical structures using AB‐type BCPs via a simple and efficient method remains challenging. Herein, a class of amphiphilic BCPs (PDenm‐b‐PACholn) is reported comprising dendronized oligoethylene glycol (Den) and cholesterol (AChol) as hydrophilic and hydrophobic moieties, respectively. By employing the collapse of PDenm blocks at a specific temperature, the fabrication of bundled fibers and multilayer vesicles is achieved with an obvious hierarchy. Different from common reversible aggregation–disaggregation processes of thermal‐responsive polymers, the ordering of the core‐forming block with liquid crystalline (LC) properties provides robustly physical cross‐linking, coupled with epitaxial growth and the lateral fusion of LC blocks, guiding the formation of stable hierarchical micellar structures. It is highlighted that the combination of temperature‐sensitive properties and LC ordering alignment offers a novel approach for constructing hierarchical structures using AB‐type BCPs via an efficient one‐step assembly method. [ABSTRACT FROM AUTHOR]