Abstract: A new ether-linked polymer (PE-A) was synthesized via the polycondensation of 1,4-dibromo-2,5-difluorobenzene with biphenol (A). The new polymer has shown a good solubility in non-polar solvents, as well as moderate thermal stability (up to 300 °C). The parent PE-A was subjected to post-functionalization modification applying the Ullmann-coupling reaction on the C-Br bonds of PE-A, where the bromo-sites have been replaced by aniline-linked moieties. The resulting polymer (PE-Ani-A) shows slight solubility in several solvents. Its thermal stability was enhanced by 36% when compared with PE-A. To ensure the significant impact of the inclusion of the aniline group on thermal stability, a thermal degradation kinetics study was performed and the Coats-Redfren and Broido theoretical models were applied to explore the degradation process. The calculated activation energy for PE-Ani-A degradation was thereby found to be higher than that of PE-A, which indicates the higher thermal stability of PE-Ani-A. For further insights into the thermal stability of the polymers, the limited oxygen index (LOI), which represents the flame-retardant property of the polymers, was calculated. The results indicate that PE-A is a promising candidate as a flame-retardant polymer (LOI = 46.7), since it has a high bromo-content. On the other hand, PE-Ani-A has a lower LOI although it has a higher thermal stability.