The thermal mechanical properties and degradation behaviors were studied on fibers prepared from two high-performance, heterocyclic polymers, poly(p-phenylenebenzobisthiazole) (PBZT) and poly(p-phenylenebenzobisoxazole) (PBZO). Our research demonstrated that these two fibers exhibited excellent mechanical properties and outstanding thermal and thermo-oxidative stability. Their long-term mechanical tensile performance at high temperatures was found to be critically associated with the stability of the C—O or C—S linkage at the heterocyclic rings on these polymers' backbones. PBZO fibers with the C—O linkages displayed substantially higher thermal stability compared to PBZT containing C—S linkages. High resolution pyrolysis-gas chromatography/mass spectrometry provided the information of the pyrolyzates' compositions and distributions as well as their relationships with the structures of PBZT and PBZO. Based on the analysis of the compositions and distributions of all pyrolyzates at different temperatures, it was found that the thermal degradation mechanisms for both of these heterocyclic polymers were identical. Kevlar®-49 fibers were also studied under the same experimental conditions in order to make a comparison of thermo-oxidative stability and long-term mechanical performance at high temperatures with PBZO and PBZT fibers. The data of two high-performance aromatic polyimide fibers were also included as references.