Twelve novel homologues with an azo linkage of the series 4-carbethoxy-[3 ' methyl-4 ' (4('')-n-alkoxy benzoyloxy)] azobenzenes have been synthesized. The methyl to n-hexyl homologues exhibit only nematic mesophases, while the n-heptyl to n-tetradecyl homologues exhibit both smectic and nematic mesophases. The n-hexadecyl homologue exhibits only a smectic mesophase. The plot of transition temperatures versus number of carbon atoms in alkoxy chain exhibits an odd-even effect for the nematic-isotropic transitions. The mesogenic behavior of present series is explained by comparing each homolog of the related mesogenic series. The synthesized compounds were characterized by a combination of elemental analysis and standard spectroscopic methods. For the exhibition of mesomorphic property the role of ester and azo linkages has been discussed. The impact of the lateral methyl group on mesomorphism is also discussed.