The preparation of activated carbon (AC) is a promising approach for the efficient utilization of Zhundong high-alkali coal. The volatilization and release of alkali and alkaline earth metal (AAEM) species can be effectively inhibited by using a lower operating temperature and a carbon matrix. However, the long time of the pyrolysis and activation process may promote the release of the AAEM from the coal during the process. Therefore, it is necessary to explore the transformation of AAEM during the preparation of AC from Zhundong high-alkali coal, and the cleanness of this process is evaluated accurately. In this study, the evolution of AAEM, distribution, and chemical speciation is characterized before and after the preparation of AC from the coal, and then thermodynamic calculations were performed using FactSage to simulate the transformation of AAEM in the coupled process of pyrolysis and activation. The results showed that in the process of AC preparation, the AAEM species inside the carbon matrix moved towards the surface of the AC with the aid of released volatiles and the activation reaction. Some Na and K species were released due to their weak binding with the carbon matrix and this resulted in the loss of Na and K content, whereas Mg and Ca were closely combined with the carbon matrix and were enriched in the AC. Furthermore, the defects and amorphous structure of the AC prepared with H₂O activation were more than that of the AC prepared with CO₂ activation, which meant that more of the AAEM species were exposed to the high temperature environment. As a result, the loss of AAEM content in the AC with H₂O activation was higher than that in the AC with CO₂ activation. In this process, a small amount of highly volatile and corrosive AAEM was produced, and the release of volatile matter and the consumption of the carbon matrix were the main factors for the AAEM loss. Therefore, the preparation of AC from Zhundong high-alkali coal is a viable method for its clean use.