Molecular motions of the luminescent liquid crystals (LLCs) show a significant effect on fluorescent emission and heat generation. In this article, a series of cyanostilbene‐based LLCs (CSs: CS1‐6, CS1‐12, CS2‐6 and CS2‐12) are synthesized to investigate how the photoluminescence and photothermal effect balanced. Among these materials, the mesogens peripheried by single alkyl chains formed enantiotropic nematic (CS1‐6) or smectic C (CS1‐12) phase with different alkyl tail lengths. When the single aliphatic chain is replaced by mini‐dendrons, room temperature (RT) monotropic hexagonal columnar phase (CS2‐12) or molecular liquid (CS2‐6) is formed. The results revealed that all these materials exhibited high efficiency emission with the highest quantum yield reaching 59.0%. The photoluminescence and photothermal effect can be effectively tuned by dispersing CSs into a commercially available RT liquid crystal matrix 8CB, which output significantly improved photothermal conversion efficiency of 63.2%. Furthermore, the photothermal can rapidly trigger the Smectic A‐Nematic‐Isotropic sequence transitions of 8CB doped with CSs. This work paves a way of adjusting the balance of photoluminescence and photothermal properties of the LLC materials.