Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three‐dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non‐contact modulation of CPL remain challenging. In this work, color‐switchable homochiral CPL films with high luminescence asymmetry factor (glum~0.11) were constructed based on the co‐assembly of a liquid crystal block copolymer (poly (ethylene oxide)‐b‐poly (methyl methacrylate) bearing cyanostilbene group) with axial chiral dinaphthalene diamine derivatives (R/S‐DINBPA). Mechanistic investigation revealed that the efficient stacking of R/S‐DINBPA with cyanostilbene groups and the liquid crystal field provide the driving force for chiral transfer and amplification. The dynamic covalent bonds of the cyanostilbene groups endow the film with chiral fixation ability and enable precise modulation of CPL luminescence bands under UV light irradiation, making it suitable for chiral patterned anti‐counterfeit encryption. This facile strategy provides a general platform for designing intelligent chiroptical materials.
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