<p>In this study, the starting compound, 25,27-diethoxycarbonylmethoxy-26,28-dihydroxycalix[4]arene was synthesized, followed by diazo coupling with 4-ethylaniline and 4-chloroaniline. Then, two novel amide-derived azocalix[4]arene compounds were synthesized via reaction with diethylenetriamine. The structures of the newly synthesized compounds (<b>6a</b>) and (<b>6b</b>) were elucidated using FT-IR and ¹H-NMR spectroscopy. These compounds are 5,17-di(4-ethylphenylazo)-25,27-bis(aminocarbonylmethoxy)-26,28-dihydroxycalix[4]arene and 5,17-di(4-chlorophenylazo)-25,27-bis(aminocarbonylmethoxy)-26,28-dihydroxycalix[4]arene, respectively. In order to compare with the thermal behaviors of these newly synthesized compounds, the starting compound was reacted with diethylenetriamine to afford 25,27-bis(aminocarbonylmethoxy)-26,28-dihydroxycalix[4]arene (<b>4</b>). Thermal decomposition profiles were investigeted for all three compounds. The measurements which were carried out under flowing nitrogen atmosphere were realized by using simultaneous differential thermal analysis and thermogravimetric analysis (DTA-TGA) apparatus. The thermal decomposition reactions of compounds (<b>6a</b>) and (<b>4</b>) are parallel to each other; these reactions consist of two consecutive stages, proceeding first with the cleavage of the ether links followed by the degradation of the entire structure. In contrast to compounds (<b>6a</b>) and (<b>4</b>), compound (<b>6b</b>) exhibits one extra degradation stage. Degradation process of this compounds begins with the removal of chlorine groups, proceeds with the decomposition of the ether links, and culminates in the total fragmentation of the all structure.</p>