Three types of Zhundong coal with different sodium contents-Shenhuazhundong coal (SHZD), Shaerhu coal (SEH), and Tianchimulei coal (TCML) were investigated to understand their slagging behaviors during circulating fluidized bed gasification (CFBG). Generally, the operational stability of Zhundong coal decreases with the rise of sodium content. Zhundong coal with low sodium content is suitable as a gasification fuel of a circulating fluidized bed. For high-sodium-content coal, agglomeration, and even defluidization, should be the focus. Agglomeration or defluidization could be alleviated or avoided by controlling the bed temperature. There is a one-to-one correspondence between temperature fluctuation and sodium content in bottom slags. Slagging is affected by sodium occurrence modes and some ash components (e.g., SiO2 and Fe2O3). Due to different contents of chemical components, especially chlorine, silicon, and sodium, the three types of Zhundong coal cause different problems. Chlorine and sodium in SEH, mainly existing as NaCl, play an important role in corroding metal walls. Microanalysis of agglomeration particles in the tests with TCML shows that the SiO2-to-Na2O ratio gradually increases from surfaces to the inner part, which confirms the effect of the Na2O-SiO2 reaction on the agglomeration. The SiO2 content in high alkali coal decisively impacts on the slagging morphology by the interaction between Na2O and SiO2 in coal itself for high-SiO2 coals or additional SiO2 from quartz sands for low-SiO2 coals.