Abstract Research on strategies to enable organic long‐persistent luminescence (LPL) emission with circularly polarized luminescence (CPL) characteristics is still very rare due to the lack of an unambiguous light‐emitting mechanism. Herein, circularly polarized long‐persistent luminescence (CPLPL) of a pair of axial chiral molecules as the guest is induced under ambient conditions by exploiting the long‐lived charge separation of the host–guest doping system, whose LPL performance can be further promoted by introducing a rigid polymer network to enhance the charge separation efficiency between host and guest. Based on these CPLPL materials, an effective combination of CPL and LPL properties that is “difficult to copy” is revealed for information encryption and anticounterfeiting applications. This work is expected to stimulate a research boom of CPLPL materials, and will hopefully promote the development of organic LPL systems.