A novel homologous series containing vinyl ester and azomethane central bridges and n-alkoxy as well as 3,4-dimethyl groups as flexible terminal/lateral groups viz. ROC6H4CH = CHCOOC6H4NCHC6H3-(CH3)(2) have been synthesized and studied with a view to establishing the relation between molecular structure and thermotropic liquid crystal (LC) properties with reference to molecular flexibility within the series. The series consists of twelve homologues (C-1 to C-16). C-6 and C-7 homologues are smectogenic plus nematogenic and C-8 to C-16 homologues are only smectogenic, and the rest of the homologues (C-1 to C-5) are nonmesomorphic. Transition temperatures and the textures of the homologues were determined using an optical polarizing microscope equipped with a heating stage (POM). The textures of a nematic phase are threaded or Schlieren and that of a smectic phase are of the A or C type. Analytical, thermal and spectral data support the molecular structures. Smectic and nematic thermal stabilities are 116.85 degrees C and 147.5 degrees C, respectively. Whose SmN/I and N-I mesophase lengths are varied between 15 degrees C to 21 degrees C and 25 degrees C to 62 degrees C, respectively. The novel compounds are compared with structurally-similar series.