Zhundong (ZD) coal is one of the abundant and promising coal fuel sources. An alternative technology for ZD coal is vital as a result of the high sodium content. Hematite-based chemical looping combustion has been proven to be an attractive ZD coal utilization technology without severe slagging and fouling problems. However, the role of ZD coal ash in the process of hematite-based chemical looping combustion is not clear. In this paper, the ZD coal ash-forming characteristic and slagging tendency are investigated experimentally. According to the comparative study on different ash-forming modes of ZD coal, the ZD coal ashforming rate is increased and less sodium is restored in ZD coal ash during the chemical looping combustion process compared to the conventional air combustion and gasification process. Some sodium in coal is fixed on the hematite surface in the form of an active phase, which is hard to migrate and release in the gas phase. On the basis of the vibrating screen experiment, the anti-wear rate (mechanical strength) of ZD coal ash from the chemical looping process is better than the air direct combustion process. In addition, the oxygen carrier properties of ZD coal ash are investigated in the thermogravimetric analyzer. ZD coal ash indeed plays the role of releasing oxygen and has the function of carrying oxygen or the oxidation regeneration function. Therefore, ZD coal ash is a kind of oxygen carrier material, and the existence of ZD coal ash promotes the progress of chemical looping combustion. Furthermore, other solid additives (pure SiO2, kaolin, bauxite, and pure Al2O3) are tested to investigate the slagging tendency of ZD coal ash in comparison to hematite. Coal ash characteristic discriminant indexes are calculated, and it is concluded that pure SiO2 shows the worst inhibition effect and pure Al2O3 possesses the strongest inhibition effect.