AbstractThermal degradation behavior of poly(1,3‐phenylene isophthalamide) and poly(chloro‐2,4‐phenylene isophthalamide) was investigated with the aid of some appropriate model compounds. The pyrolysis products of these materials were identified by gas chromatography (GC), gas chromatography/Fourier transform infrared spectroscopy (GC/FT‐IR), and gas chromatography/mass spectrometry (GC/MS). The residual chars were characterized by IR spectroscopy. Thermogravimetric analysis (TGA) was applied to study the effect of end‐group concentration on the degradation characteristics of the two polyamides. Kinetic parameters that describe the thermal degradation of the polyamides were also evaluated by TGA. The results of this investigation suggest that the thermal decomposition of these aromatic polyamides involves homolytic as well as hydrolytic cleavages of the amide units.