Eleven members of a novel azoester homologous series entitled 2-[4'-n-alkoxy benzoyloxy]-naphthylazo-2 ''-methoxybenzenes are reported. The methyl to n-butyl homologues are nonmesomorphic, but the other homologues are mesomorphic. The pentyl, hexyl, and hexadecyl homologues exhibit only the nematic phase. The octyl, decyl, and dodecyl homologues exhibit a smectic phase in addition to the nematic phase, however, the tetradecyl homologue exhibits only a smectic phase. An odd-even effect with alternation of transition temperatures is observed for the nematic-isotropic transition curve. The average thermal stability and liquid crystal behavior for the smectic and nematicmesophases are 99.5 degrees and 132.0 degrees, respectively, and the mesomorphic properties are compared with structurally isomeric homologous series. Analytical data confirms the molecular structures of the novel materials. The textures from optical polarizing microscopy of the nematic and smectic phase show the expected Schlieren and focal conic appearances, respectively.