Agglomeration of bed material may cause severe operating problems during fluidized bed combustion. The attack or coating layers that are formed on the bed particles during combustion play an important role in the agglomeration process. To reduce bed agglomeration tendencies, alternative bed materials may be used. In this paper, bed agglomeration characteristics during the combustion of biomass fuels using a relatively new bed material (iron blast-furnace slag) as well as ordinary quartz sand were determined. Controlled agglomeration tests lasting 40 h, using five representative biomass fuels (bark, olive residue, peat, straw, and reed canary grass) were conducted in a bench-scale fluidized bed. The bed materials and agglomerates were analyzed using SEM/EDS and X-ray diffraction. Chemical equilibrium calculations were performed to interpret the experimental findings. The results showed that blast-furnace slag had a lower tendency to agglomerate than quartz sand for most of the fuels. The quartz particles showed an inner attack layer more often than did the blast-furnace slag. The blast-furnace slag had a lower tendency to react with elements from the fuel. The outer coating layer had similar characteristics and thickness for both bed materials when the same fuel was combusted. However, the inner attack layer thickness was larger for quartz particles. SEM/EDS analyses of the agglomerates showed that the inner Ca-K-silicate-rich attack layer was responsible for the agglomeration of quartz sand. The composition of blast-furnace slag agglomerate was similar to the outer coating layer. Chemical equilibrium calculations showed that the original composition of the blast-furnace slag was close to the equilibrium composition, and hence there was no major driving force for reactions between that bed material and K and Ca from the fuel. The homogeneous silica-rich attack layer (with a low melting temperature) was not formed to the same extent for blast-furnace slag, thus explaining the lower bed agglomeration tendency.