The main objective of this paper is to study the thermal stability of some aromatic copolyethers containing a propylenic spacer. Some of the investigated copolyethers displayed a liquid crystalline (LC) behavior, with the presence of the mesogenic groups in the main chain, inducing high values of the thermal transition temperatures. As a consequence, a thermal stability study was necessary to establish the maximum temperature value for the LC behavior characterization. A thermal degradation mechanism is proposed, taking into consideration the azobenzenic unit as the weakest link in the polymer chain and thus, the starting point of the thermal degradation process. The degradation mechanisms were correlated with the chemical structure and the polarity and conformation of the chains. Conformational analysis was performed using molecular simulations. Freeman-Caroll and Coats-Redfern methods were used to calculate some kinetic characteristics.