The modes of occurrence, migration, and evolution pathways of lithium (Li) and gallium (Ga) during combustion of an Al-rich coal from Inner Mongolia, China, were investigated using methods of simulated combustion experiments, the sequential chemical extraction procedure (SCEP), and the thermodynamic equilibrium calculation. Mineralogical and chemical compositions of the feed coal and combustion ash were analyzed by X-ray fluorescence (XRF), X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS), and scanning electron microscopy (SEM). The study reveals that Li and Ga are significantly enriched in the ash after combustion, with the contents reaching up to 1086 μg/g and 133 μg/g, respectively. The primary modes of occurrence of Li and Ga in the ash are quartz and aluminosilicates, and sulfides, respectively. Li, in the form of LiAlSi₄O₁₀ (s), primarily occurs in hematite, glass, and quartz below 800 °C. However, it migrates into the glass phase, mullite, and quartz above 1000 °C. On the other hand, Ga exists as Ga₄S₅ (s) and transforms into Ga₂S (g) as the temperature rises from 800 °C to 1000 °C, maintaining this gaseous form until 1200 °C. Ga₄S₅ (s) predominantly occurs in the glass phase at 600 °C, whereas mullite and quartz become its dominant modes of occurrence in industrial combustion ashes and ashes obtained from simulated combustion above 600 °C.