In order to investigate the influence of the terminal substitution on mesomorphism, the newly synthesized homologues series based on azoester have been synthesized. The influence of the structure of the mesogenic core has been present in this study, effect of hydrocarbon chain length and flexibility at terminal side effect on mesomorphism was represents in this case. In this investigation, we represent a series consisting of thirteen (C-1-C-18) homologue. In which, C-1 to C-3 homologue are nonmesomorphic. While C-4-C-18 shows smectic as well as nematic mesophase enantiotropically. Analytical and spectral data confirmed the molecular structures of homologues. All these compounds were characterized by elemental analysis and Fourier transform infrared [FTIR] and H-1 NMR. Their mesomorphic properties were measured by optical polarized light microscopy and differential scanning calorimetry (DSC) and PXRD.