A novel azoester homologous series of laterally and terminally substituted viz, RO-C6H4-CH=CH-COO-C6H3-(CH3) -N=N-C6H4-Cl is synthesized, characterized and studied with a view to understand and establish the relation between molecular structure and thermotropic liquid crystalline property of its homologs. Series consists of twelve homologs. LC properties commence from very first member of a series and continue up to last homolog as enantiotropic nematic with absence of smectic property even in the monotropic condition. Transition temperatures of homologs were determined by polarizing optical microscopy equipped with a heating stage. The transition curves Cr?N and N?I behaved in normal manner. Thermal stability for nematic is 196.7 degrees C whose mesophaselength ranges from 35 degrees C to 131 degrees C.