Two new aromatic-aliphatic polyamides containing azo linkage in the main chain based on 2,2'-dimethyl-4,4'-diaminoazobenzene and adipic/2-chloro-5-methyl-1,2-dioic acid (alpha-chloro-delta-methyl adipic acid) were synthesized and analyzed by thermogravimetry and films were cast. Also three polymers obtained from condensation of 4,4'-azodibenzoic acid/adipic acid and 2,2'-bis [4-(p-amino phenoxy) phenyl] propane/4,4'-diaminoazobenzene Were studied in terms of mechanical and morphological properties. Film studies were carried out interms of tensile property, scanning electron microscope, dielectric, microwave, and X-ray diffraction pattern. Thermal studies have been done using thermogravimetric analysis, differential thermal analysis, and pyrolysis-mass spectral data. The results were correlated with structure and orientation of the molecules. (C) 2004 Wiley Periodicals, Inc.