An effective bed material is crucial to remit slagging/agglomeration for high-sodium lignite during circulating fluidized bed (CFB) gasification. In this study, the exploration of effective bed material for use as slagging/agglomeration preventatives of high-sodium lignite mined from Zhundong district was conducted in a 0.4 T/D CFB test system. Three mineral materials, SiO2-based quartz sand, Al2O3-based corundum and CaO/Fe2O3-rich boiler ash collected from bottom ash of a CFB industrial boiler, were selected as the potential bed material. Their impacts on the de-fluidization tendency, transformation and migration of alkali metals, priority of reactions involving sodium-based species, formation of liquid slags and ash fusibility were investigated through the characterization of ash samples and thermodynamic equilibrium calculation by Factsage 6.1. The particle-size analysis results presented the improvement of three bed materials in the growth of ash particles followed the order of quartz sand > corundum > boiler ash. This order was ascribed to their reaction priority with sodium-based compounds in coal and the chemical property (mainly referring to ash fusibility) of corresponding products. Generally, reactions between sodium-based species and minerals (Al2O3 and SiO2) were the main way of sodium retention within the ash in gasifier. As boiler ash was used, however, Al2O3 and SiO2 preferentially reacted with the CaO enriched in boiler ash rather than sodium-based species in coal, resulting in very low sodium retention. Under such circumstances, computing results suggested the ash in gasifier could withstand higher gasification temperature, consistent with the measured results of ash fusibility. Additionally, the gasification temperature operating range could be largely widened by simply increasing CaO/Fe2O3 content in gasified ash. Therefore, boiler ash is an effective and low-cost bed material for use as the slagging/agglomeration preventative of high-sodium lignite during CFB gasification.