The mesomorphic stability and optical activity of new group-based benzotrifluoride liquid crystals, (E)-4-(((4-(trifluoromethyl) phenyl) imino) methyl) phenyl 4-(alkyloxy)benzoate, orIn, were investigated. The end of the molecules connected to the benzotrifluoride moiety and the end of the phenylazo benzoate moiety have terminal alkoxy groups which can range in chain length from 6 to 12 carbons. The synthesized compounds’ molecular structures were verified using FT-IR,1H NMR, mass spectroscopy, and elemental analysis. Mesomorphic characteristics were verified using differential scanning calorimetry (DSC) and a polarized optical microscope (POM). All of the homologous series that have been developed display great thermal stability across a broad temperature range. Density functional theory (DFT) determined the examined compounds’ geometrical and thermal properties. The findings showed that every compound is entirely planar. Additionally, by using the DFT approach, it was possible to link the experimentally found values of the investigated compounds’ investigated compounds’ mesophase thermal stability, mesophase temperature ranges, and mesophase type to the predicted quantum chemical parameters.