By combining [Mo6I8(CnF2n+1COO)(6)](2-) (n = 1, 2, 3) nanocluster units with liquid crystalline ammonium cations, a new series of hybrid materials is developed that show a nematic liquid crystal phase, the most fluid of all LC phase, on a large range of temperatures including room temperature. The photophysical studies performed in the LC state show that these self-assembled hybrid materials emit in the red-NIR with absolute quantum yields up to 0.7 and show a very good photostability under continuous irradiation. They are further integrated up to 20 wt% in E7, a well-known nematic commercial LC mixture. Mixtures are investigated in terms of homogeneity and stability to select the best suitable candidate for the design of electro-controlled devices. Studies of optical switching, contrast, viscosity, and behavior toward an electrical stimulus demonstrate the high potential of these hybrid materials in the fields of photonic or optoelectronic.