A homologous series with carboxylate ( -COO-) and azo (-N=N-) as central groups have been synthesized by treating 4-n-alkoxy benzoyl chloride with 4-Hydroxy-3-methoxy phenyl azo-4’- chlorobenzene. The first and second members of the series are non-mesomorphic. The nematic property is exhibited by the propyl to hexadecyl derivatives. Polymesomorphism commences from Butyl derivative of the series enantiotropically. The mesogenic properties of the present series are compared with those of other structurally similar mesogenic series. Odd –even effect is observed for smectic nematic and nematic isotropic transition curve behaving in normal manner. Mesomorphic range is between 260C to 640C and series is of middle ordered melting type without any predominancy of either smectic or nematic property. Texture of nematic mesophase is of threaded type and that of smectic mesophase is focal conic fan shaped of the type Smectic-A or Smectic-C as determined by missibility method. analytical data support the structures of molecules. Transition temperatures are determined by hot stage polarizing microscope.