Gallium (Ga) and germanium (Ge) critical elements have a wide range of applications and market value. Extracting critical elements from coal gangue and combustion products can alleviate pressures on primary mining resources. Understanding the transformation behavior of Ga and Ge during coal gangue combustion processes is significant for resource utilization and environmental protection. Coal gangue from Xing’an League, Inner Mongolia, was chosen to explore how combustion temperatures (600 °C to 1000 °C) and particle sizes (50, 80, 10, 140, and 200 mesh) influence Ga and Ge migration during combustion. Techniques such as ICP-MS, XRD, XRF, SEM, TG−DSC, and sequential chemical extraction were employed to analyze the transformation of minerals and to quantify the contents and occurrence forms of Ga and Ge. Smaller gangue particle sizes were associated with higher concentrations of Ga and Ge. Approximately 99.19% of Ga and Ge in coal gangue were found in the residual, organic/sulfide-bound, and metal-oxide-bound modes. High temperatures promoted element volatilization and changed the reactions and interactions between elements and minerals. As combustion temperatures rose from 600 °C to 1000 °C, Ga and Ge contents in the products declined progressively. Under high temperatures, minerals like kaolinite, illite, and pyrite in gangue converted to silicate glass phases, mullite, and hematite. Minerals like kaolinite, calcite, and pyrite melted, leading to increased cohesion and agglomeration in the products. Over 90% of Ga and Ge in the combustion products existed in the residual, organic/sulfide-bound, and metal-oxide-bound forms. Moreover, Ga was enriched in combustion products, with its content exceeding critical extraction levels. The results may provide a useful reference for developing critical elements enrichment, extraction, and separation technologies from coal gangue.