When preventing spontaneous combustion disasters in extinguished coal fire zones, the influence of the tar re-ignition phenomenon is often overlooked. Therefore, in this study, using thermogravimetric analysis and high-temperature (630 °C) in-situ infrared technology, the combustion reactivity and real-time evolution mechanism of key functional groups for tar were deeply discussed under oxygen-lean conditions. Additionally, a novel two-step baseline drift correction method for spectral graphs at high temperatures is proposed. The results showed that tar combustion could be divided into two stages: pyrolysis-volatilization mass loss and crosslinked structure oxidation combustion. Reduced oxygen concentration limits the violent and stable rapid combustion of tar-crosslinked structures and reduces the re-ignition tendency of tar. Among, with a decrease in oxygen concentration, H (burnout performance), Cb (the reaction ability in the early stage of ignition) and S (overall combustion performance) decreased, while Ti (mass loss endpoint temperature), Th(burnout temperature), and HF (combustion stability) increased. This provides information for the selection of a reasonable process to prevent tar re-ignition. The contents of methylidene and aldehyde carbonyl in tar increased by approximately 2 and 3.7 times, respectively, compared to those of raw coal. In the first thermal decomposition stage of tar, the aromatic hydrocarbons were relatively stable under the action of the structural framework, whereas aliphatic hydrocarbons continued to decrease. Before burnout, a decrease in oxygen concentration increased the crosslinking ability of tar and delayed the tar burnout process. The contents of aromatic hydrocarbons and aldehyde groups are highly sensitive to the evolution of the oxygen concentration. Specifically, the Kubelka–Munk value of the aromatic hydrocarbons increased from 0.015 to 0.10, while that of aldehyde carbonyl groups increased from 0 to 0.23. Additionally, in the early stage of tar combustion, the volatile mass loss was basically not affected by the time-scale effect, and mass loss endpoint residual mass was approximately 48.11 %. In the later stage of tar combustion, owing to the cumulative of time-scale effect, the tar re-ignition tendency increased, H, Cb, and S increased, and HF decreased from 1.388 to 1.098. This research is helpful guiding disaster prevention and control of tar re-ignition in a fire area, which leads to reburning in the surrounding area.