The increasing demand of liquid crystalline materials in various fields of applications has inspired the present investigation. A mesogenic homologous series, 4-(4 '-n-alkoxy benzoyloxy)-3-chloro phenylazo-2 ''-chlorobenzenes, of twelve homologues has been synthesized. All the members of the series are either monotropically or enantiotropically mesogenic except the first member of the series. The nematic mesophase commences from the ethyl derivative and goes to the dodecyl derivative of the series. Tetradecyl and hexadecyl derivatives show a monotropic smectic phase. The nematic mesophase shows a threaded texture, while the smectic mesophase shows a focal-conic-fan-shaped texture. Polymesomorphism is not displayed by any member of the series. The solid-isotropic or solid-mesomorphic transition curve follows a zigzag path of falling and rising tendency as the series is ascended. The usual odd-even effect is observed in the nematic-isotropic transition curve with alternation of transition temperature. Transition temperatures are observed through a polarizing microscope with a heating stage. Analytical data support the structure of the molecules. The average thermal stability and mesomorphic properties of the series are compared with structurally similar other homologous series. Group efficiency order for the smectic and the nematic phases is suggested.