Description:
<jats:title>Abstract</jats:title><jats:p>A major trade‐off in the field of circularly polarized luminescence (CPL) of pure organic materials is that the large luminescence dissymmetry factor (<jats:italic>g</jats:italic><jats:sub>lum</jats:sub>) usually gives rise to the suppression of luminescence efficiency (<jats:italic>Φ</jats:italic><jats:sub>PL</jats:sub>). Here, a supramolecular self‐assembled system, driven by arene–perfluoroarene (AP) interactions of chiral polycyclic aromatic hydrocarbons (PAHs) and octafluoronaphthalene (<jats:bold>OFN</jats:bold>), is reported to provide a solution to this problem. Two kinds of chiral PAHs based on pyrene and anthracene could co‐assemble with <jats:bold>OFN</jats:bold> in hybrid solvents to form long‐range‐ordered AP assemblies. The detailed process of AP interaction driving self‐assembly was verified by morphological measurements and fluorescence spectra. The AP assemblies exhibited chirality amplification not only in the excited state but also in the ground state. In addition, the AP assemblies showed an enhanced luminescence efficiency compared with the individual chiral PAHs due to the energy‐barrier effect of <jats:bold>OFN</jats:bold>. The present strategy based on AP interactions could be applied to boost the development of highly efficient CPL‐active materials.</jats:p>