Luminescent liquid crystals (LLCs) have attracted significant interest in organic optoelectronic applications owing to their ordered alignment and luminescence properties. In this study, a series of dicyanodistyryl-benzene-based calamitic molecules, (2Z, 2'Z)- 2,2'-(1,4-phenylene)bis(3-(4-(N-alkoxy)phenyl)acrylonitrile (Cn), are reported. In addition, the mesomorphism and luminescence properties of the as-prepared Cn were evaluted. With increasing chain length to six methylene groups, Cn formed a smectic C liquid crystal phase. For C8, C12, and C18 with long flexible chains, a chiral smectic C (SmC*) phase formed because of the asymmetrical twisted configuration. The results demonstrated that the compounds are aggregation-induced enhanced emission-active materials, and the suspensions of C12 and C18 in a THF/H2O mixture exhibit green, yellow, and orange emission colors depending on the self-assembled structure, which can be modulated by controlling the aggregation speed.