Circularly polarized long-lived fluorescent materials show unique application values in circularly polarized organic light-emitting diodes, advanced anti-counterfeiting materials, and so forth. However, the circularly polarized long-lived fluorescent materials with large luminescence dissymmetry factor (glum) values and long fluorescence lifetime are rarely reported. In this article, we propose to prepare circularly polarized long-lived fluorescent materials based on triplet-to-singlet Förster-resonance energy transfer (TS-FRET) mechanism. We have prepared circularly polarized long-lived fluorescent luminescent materials with large glum values, long fluorescence lifetime, high luminescent quantum yield and large Stokes shift by blending chiral room temperature phosphorescent liquid crystal Chol-C6-DF with achiral fluorescent component Br–C6-Nap. Attributed to the effective TS-FRET process between Chol-C6-DF and Br–C6-Nap, the obtained doped films show long fluorescence lifetime. When the doping amount of Br–C6-Nap is 2 wt%, the fluorescence lifetime can achieve 103 ms. All obtained doped films exhibit high glum values attributed to selective reflection of chiral liquid crystals. As the doping amount of Br–C6-Nap increases, the |glum| value first increases and then decreases, with a maximum of 1.45. In addition, the doped films also possess high solid-state luminescence quantum yield and large Stokes shift, with a maximum value of 54 % and 284 nm, respectively.