Two new nonsymmetrical mesogenic homologous series of terminal substituent ether (series [V-n]) and carboxy (series [VIn]) incorporating azobenzene and 1,3,4-oxadiazole group were synthesized. Both series have been All compounds thus isolated were purified and characterized by elemental analysis, Fourier Transform Infrared Spectroscopy, 1H NMR, along with thermal analysis and texture observation using Differential Scanning Calorimetry (DSC) and Polarizing Optical Microscopy (POM), respectively. All compounds of the first series exhibited liquid crystalline properties. The homologues [V-1]-[V-3] display a nematic mesophase, the compounds [V-4]-[V-7] exhibit a dimorphism behavior, nematic (N) and smectic A (SmA) mesophases, the compounds [V-8] and [VI9] display enantiotropic smectic A and C (SmA and SmC) phases and the last homologue [V-12] exhibits only a smectic C mesophase. All compounds of the second series [VIn] also show mesomorphic behavior, the compounds [VI1]-[VI3] and [VI5] display the nematic mesophase, the homologue [VI7] exhibits dimorphism behavior, nematic, and smectic A (SmA). The mesomorphic behavior has been analyzed in terms of structural property relationships.