<p>The present work aims to provide preliminary support and research foundation for developing integrated technology of CO₂ utilization and tar-rich coal pyrolysis to produce high-value chemicals and fuels. The chemical properties of tar produced by tar-rich coal pyrolysis under traditional N₂ and N₂/CO₂ atmospheres were investigated in a fixed-bed reactor at different temperatures (600°C–800°C) and atmospheric pressures. The results showed that tar-rich coal pyrolysis under CO₂ atmosphere can promote tar production (mass fraction 8.42% increased) compared with that of traditional pyrolysis (under N₂), with the maximum value up to 21.26% (in weight). It should be noted that the generation of coal tar and CO small molecule gas can be promoted by increasing the concentrations of CO₂ in pyrolysis atmosphere gases. GC-MS and simulated distillation results showed that the CO₂ atmosphere can promote the production of light oil components such as phenols, alcohols, and olefins, while inhibiting the production of heavy components such as asphalt simultaneously. Elemental analysis results showed the H/C ratio of coal tar increased under CO₂ atmosphere indicating that the high quality of coal tar is improved, which is consistent with that of simulated distillation and GC-MS test. Finally, a possible reaction pathway of tar-rich coal under CO₂ atmosphere pyrolysis is also proposed.</p>