Spontaneous Symmetry Breaking to Amplified Chirality: Biomimetic Helical Nanofibers for High‐Performance Circularly Polarized Luminescence

Helical micro‐nanomaterials with intelligently controllable, multi‐color circularly polarized luminescence (CPL) have garnered significant interest for their promising applications in chiral chemistry, photonics, and electronics. However, the precise and convenient fabrication of multi‐color and white CPL‐active flexible nanofibers featuring continuous helical topological structures remains challenging, particularly in the deformable solid nanomaterials. In this study, we employed a soft (polyurethane elastomer)/ hard (conjugated helical polymer/ cellulose/fluorescent dyes) bicomponent electrospinning strategy, through which helically chiral luminescent nanofibers with predominant single‐handedness were spontaneously formed due to intercomponent strain mismatch. By constructing hierarchical helices from the molecular to the mesoscopic scale, we achieved a biomimetic chiroptical flexible material that exhibits unique chirality amplifications. This work reveals a previously unreported synergistic strategy for the construction of mesoscopic chiral luminescent helical nanofibers. Furthermore, owing to the excellent flexibility and designability of electrospun nanofibers, as well as the unique physical and optical properties provided by chiral helical polymers and mesoscopic helical micro‐and nanofibers, the prepared multicolor and white CPL‐active nanofibrous films demonstrate promising application prospects in circularly polarized LED devices, blue‐light blocking films, and even as substitutes for flexible liquid crystal cells—highlighting the innovation and potential of this research system.