A new homologous series: isopropyl-p-[p(/)-n-alkoxy cinnamoyloxy] cinnamates was synthesized and studied with a view to understanding and establishing the relation between liquid crystal property and molecular structure. Twelve homologues were synthesized. Methyl to butyl homologues are not liquid crystals, while pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl derivatives are enantiotropic liquid crystal in nature with nematogenic character. Smectogenic character is totally absent. A phase diagram is obtained by plotting a graph of transition temperatures versus number of carbon atoms is n-alkyl chain of left n-alkoxy terminal end group. Solid-isotropic or solid-nematic transition curve rises steeply from methyl to propyl derivatives and falls to pentyl homologue through butyl homologue, and follows a zigzag path of rising and falling values as the series is ascended. Nematic-isotropic transition curve shows descending tendency as series is ascended in a normal manner with exhibition of odd-even effect. Smectic mesophase does not appear even in the monotropic condition. Phase transition temperatures are determined by hot stage polarizing microscope. Analytical data support the structure of molecules. Texture of nematic mesophase is of threaded type. Mesomorphic properties are compared with structurally similar homologous series.