Hierarchical Self‐Assembly Boosts Circularly Polarized Luminescence of π‐Extended Binaphthyl Amphiphiles

ABSTRACT Circularly polarized luminescence (CPL) from small organic molecules remains challenging to achieve with high efficiency. Here, we present a design strategy for sequential CPL amplification in π‐extended binaphthyl amphiphiles. A trifluoroacetic acid‐catalyzed alkyne cyclization introduces rigid π‐extension, reinforcing circular dichroism (CD) and CPL at the molecular level. Driven by amphiphilicity, the cyclized products undergo hierarchical self‐assembly in methanol–water mixtures, evolving from nanoscale aggregates to ordered superstructures. This multilevel organization amplifies molecular chirality and exciton coupling, delivering a dissymmetry factor (| g lum |) of up to 7.0 × 10 −2 . In contrast, non‐cyclized precursors show only weak chiroptical activity, underscoring the essential role of π‐extension and assembly‐driven amplification. These findings demonstrate that hierarchical self‐assembly serves as an effective method for regulating chiroptical properties and advances the development of high‐performance organic CPL materials.