Long-term combustion of low-quality coal may release hazardous elements into the environment causing serious environmental problems. This phenomenon is particularly prevalent in the Three Gorges Region of Southwest (SW), China. Cadmium (Cd), as well as other harmful elements are found to be highly enriched in coals and supergene environments in this area. In the existing literature, the behavioral issue of emission and transformation of the elevated trace elements during simulated household stove combustion from Cd-rich inferior coal remains unknown. This study investigated the emission of toxic elements, mineral assemblages, and provided technical guidance for reducing pollution by means of optimization combustion tests on inferior coals. The research may improve the understanding of geochemical characteristics from toxic elements emission in coal combustion endemic diseased areas. For this purpose, a series of simulated coal combustion experiments were conducted to reveal the release, mobility, and distribution of elevated elements in Cd-rich coal combustion products. The results showed that Cd, Mo, Cr, Cu, Zn, As, and Sb were significantly enriched in the inferior coals of the study area. Furthermore, large amounts of toxic elements were released as fly ash into the environment during the combustion process. In particular, combustion conditions played an important role in the emission and transformation of elevated elements. For example, higher temperatures promoted the release of Cd, Sb, Zn, and Tl into the environment. Oxygen-deficient combustion was found to liberate more Cd, Sb, and Tl to the atmosphere and generated complex mineral assemblages of lizardite, calcite, dolomite, forsterite, and enstatite. Moreover, toxic elements were found to be absorbed in the fine particle matter of fly ash from the endemic fluorosis area of SW, China. The findings of this work may aid to control the emission of toxic elements from inferior coals and mitigate the effect of toxic elements in the environment to protect human health.