Here, a photoluminescent liquid crystal that exhibits a change of emission color on the metastable–stable phase transition induced by external stimuli is prepared. A 2,6-diethynylanthracene derivative with amide groups and dendritic side chains exhibits a columnar phase on slow cooling from the isotropic phase and shows blue emission in this columnar phase. In contrast, a cubic phase is obtained by rapid cooling from the isotropic phase. In the cubic phase, the 2,6-diethynylanthracene cores form excimers, resulting in yellow emission. While the columnar phase is a stable liquid-crystalline (LC) phase, the cubic phase is a metastable LC phase. It is found that a change of the photoluminescent color from yellow to blue is observed on the cubic-columnar phase transition induced by heating or mechanical shearing for this 2,6-diethynylanthracene derivative in the cubic phase. This change of photoluminescent color is ascribed to the inhibition of excimer formation on the metastable–stable LC phase transition.