The chemical-kinetic characteristics of oxy-coal MILD combustion under different initial temperature and oxygen concentration were studied numerically. Aromatic benzene was considered representative for coal molecule. A unique reaction pathway under low oxygen concentration was obtained, the activation energy and reaction rate constant of involved elementary reactions were calculated through classic transition state theory (TST). The results show that low oxygen concentration and high temperature is advantageous for thickening flame front as well as slowing down flame propagation; as oxygen concentration and temperature increase, the global activation energy increases with greater slope; the decomposition of C5H5 dominates under high oxygen concentration, while the decomposition and oxidation of C5H5 become equally important as oxygen concentration decreases, leading to a new pathway that the complexity of overall chemical reactions develops; the radical CH2CHO is easily trigged under low oxygen concentration, its decomposition reaction dominates in the unique pathway C5H5→C5H4O→c-C4H5CH2CHO→CH3 due to larger activation energy, where more CO escapes. The simulation results have theoretical referencing value, laying foundations for the further practical work.