A novel cinnamate ester homologous series has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on liquid crystal (LC) properties with a focus on the highly polar methoxy group as a lateral substituent. The series consists of twelve homologs; of which C-1-C-5 are nonmesogenic, and the rest of the homologs are enantiotropically smectogenic or and nematogenic. The texture of nematic phases is threaded or Schlieren and that of the smectic is either smectic A or C, as recognized and determined through an optical polarizing microscope equipped with a heating stage. The Sm-N I and N-I transition curves exhibit odd-even effects and behave in normal manner. The Cr-I M behaves in normal manner. Analytical and spectral data confirm the molecular structures of homologs. The average thermal stabilities for smectic and nematic are 125.3 C and 129.8 C, respectively, whose total mesophase length varies from 13 C to 51 C. Some LC properties of present series are compared with the structurally similar known series.