Abstract

Abstract Circularly polarized room‐temperature phosphorescence (CPRTP) simultaneously featuring multiple colors and extremely high dissymmetry factor ( g lum ) is crucial for increasing the complexity of optical characteristics and advancing further development, but such a type of CPRTP is still unprecedented. The present work develops an effective and universal strategy to achieve full‐color CPRTP with ultra‐high g lum factors in a polymeric cholesteric superhelix network, which is constructed by cholesteric liquid crystal polymer and chiral helical polymer (CHP). Taking advantage of the high helical twisting power of CHP, the resulting polymeric cholesteric superhelix network exhibits remarkable optical activity. Significantly, by adopting a simple double‐layered architectures consisting of the cholesteric superhelix film and phosphorescent films, blue‐, green‐, yellow‐, and red‐CPRTP emissions are successfully obtained, with maximum | g lum | values up to 1.43, 1.39, 1.09 and 0.84, respectively. Further, a multilevel information encryption application is demonstrated based on the multidimensional optical characteristics of the full‐color double‐layered CPRTP architectures. This study offers new insights into fabricating polymeric cholesteric superhelix with considerable CPRTP performance in advanced photonic applications.