LAUSR

Abstract Controllable construction of diversiform topological morphologies through supramolecular self‐assembly on the basis of single building block is of vital importance, but still remains a big challenge. Herein, a bola‐type supra‐amphiphile, namely DAdDMA@2β‐CD, is rationally designed and successfully prepared by typical host–guest binding β‐cyclodextrin units with an aggregation‐induced emission (AIE)‐active scaffold DAdDMA. Self‐assembling investigation reveals that several morphologies of self‐assembled DAdDMA@2β‐CD including leaf‐like lamellar structure, nanoribbons, vesicles, nanofibers, helical nanofibers, and toroids, can be straightforwardly fabricated by simply manipulating the self‐assembling solvent proportioning and/or temperature. To the best of knowledge, this presented protocol probably holds the most types of self‐assembling morphology alterations using a single entity. Moreover, the developed leaf‐like lamellar structure performs well in mimicking the light‐harvesting antenna system by incorporating with a Förster resonance energy transfer acceptor, providing up to 94.2% of energy transfer efficiency.