This paper presents a complex system exhibiting intense circularly polarized ultraviolet luminescence (CPUVL) with a large luminescence dissymmetry factor (*g<sub>lum</sub>*), enabling chiral UV light-triggered enantioselective polymerization. The system integrates sensitized triplet-triplet annihilation upconversion and CPL, achieving both visible-to-UV upconversion emission and upconverted circularly polarized ultraviolet luminescence (UC-CPUVL). Dispersing this system in room-temperature nematic liquid crystal amplifies the *g<sub>lum</sub>* value of UC-CPUVL, which then triggers enantioselective diacetylene photopolymerization. This work advances functional applications of CPL-active materials.
