Paper
Abstract Self‐assembly in supramolecular chemistry is crucial for nanostructure creation but faces challenges like slow speeds and lack of reversibility. In this study, a novel comb‐like polymer poly(amide sulfide) (PAS) based on thiolactone chemistry is reported, which rapidly self‐assemble into stable nanofibers, offering excellent robustness and reversibility in the self‐assembled structure. The PAS backbone contains pairs of amide bonds, each linked to an alkyl side chain in a controlled 2:1 ratio. The polymer rapidly forms fibrillar micelles driven by the hydrophobic side chains and then undergoes hydrogen‐bonded cross‐linking between the main‐chain amide bonds to form stable nanofibers. N, N‐dimethylacetamide/LiCl solution allows for reversible regulation of nanofiber self‐assembly, without altering the fiber properties. It is anticipated that this line of research will enrich the field of macromolecular self‐assembly with important advances toward the realization of ultrafast, robust, and reversible self‐assembly systems.