Vinyl carboxy central group containing a novel chalconyl ester homologous series: RO.C6H4.CH CH.COO.C6H4.CH CH.CO.C6H4.I (para) have been synthesized and studied with a view to understand and establish the relation between thermotropic liquid crystalline (LC) behaviors and the molecular structure. Novel chalconyl ester homologous series consists of thirteen homologs (C-1-C-18). C-1-C-3 homologs are nonmesogenic, C-4 homolog is enantiotropic nematogenic and the rest of the homologs (C-5-C-18) are enantiotropically smectogenic plus nematogenic. Phase transition temperatures and textures of LC phase were determined by an optical polarizing microscopy (POM) equipped with a heating stage. Cr-M/I, Sm-N, N-I transition curves in a phase diagram behaved in normal manner. Sm-N and N-I transition curves exhibited odd-even effect from C-4-C-10 or nearby C-10 homolog. Textures of nematic phase are threaded or Schlieren and that of the smectic phase are of the type smectic A or C. Analytical and spectral data confirms the molecular structure of homologs. Thermal stabilities for smectic and nematic mesophases are 155.0 and 180.7, respectively, and their corresponding mesophaselengths are varied from minimum to maximum at 17.0 degrees C-39.0 degrees C as well as 15.0 degrees C-30.0 degrees C. Thus, it is middle ordered melting type series. The group efficiency orders derived on the basis of smectic and nematic thermal stabilities are as under: Sm: -C6H4.I > -C6H4.Cl > -C4H3S and N:- C6H4.I > -C6H4.Cl > -C4H3S from comparative study of structurally similar analogous series