A novel homologous series 4-[4 '-n-alkoxy cinnamoyloxy] benzyl cinnamates consisting of 11 homologs was synthesized and studied with a view to understanding and establishing the relation between molecular structure and mesomorphic behavior of a substance. Mesomorphic behavior of the series commences from the third homolog and then continues until the last hexadecyloxy homolog. The first and second members of a series are non-mesomorphic. Nematogenic mesophase formation is observed from the propoxy homolog to the hexadecyloxy homolog, but the smectogenic mesophase formation is observed from the hexyloxy homolog to the tetradecyloxy homolog. All mesomorphic transitions are enantiotropic in nature. Transition temperatures were determined by an optical polarizing microscopy equipped with a heating stage. The textures of the nematic mesophase are threaded or Schlieren in type and that of the smectic mesophases are focal conic fan shaped of the smectic A or smectic C type. A phase diagram of the series shows a normal behavior of the transition curves with a minor abnormality of the last three homologs for the nematic-isotropic transition curve. The average thermal stability for smectic and nematic mesophases is 176.0 degrees C and 219.3 degrees C, respectively. Analytical and spectral data agree with the molecular structures of homologs. Mesomorphic phase length varies between 22 degrees C and 76 degrees C. Smectic phase length varies from 6 degrees C to 33 degrees C and nematic phase length varies from 22 degrees C to 54 degrees C. Thus, the novel present series is predominantly nematogenic and partly smectogenic. Mesomorphic properties of the novel series are compared with structurally similar other known homologous series.