A coordination complex, Eu(C 12 C 12 dbm) 3 (phen), with strong emission and a high quantum yield (QY ∼ 51.9%) was synthesized. The Eu III complex, as a fluorescent emitter, was embedded in cholesteric liquid crystal polymer networks (CLCNs). A series of free-standing Eu III -CLCN films were obtained, generating a typical sharp emission band corresponding to the Eu III complex. Tunable handedness of circularly polarized luminescence (CPL) with high |g lum | values (up to 0.63) was observed. A series of CPL-active CLCN-coated PET films were also prepared (|g lum | values up to 0.63), which can be used for largearea preparations. Moreover, by stacking an emitter-embedded PMMA layer and a CLCN layer, a composite system was built, and a large |g lum | value (∼1.42) was achieved. Fluorescence patterns were prepared, and distinct images of CLCN films were recognized under both daylight and UV light. This work not only demonstrated that coordination compounds could be incorporated with CLCN films to prepare CPL-active materials with high |g lum | values but also provided a new perspective for emissive CLCN materials used for anticounterfeiting and encryption.