The major ash-related problem encountered in fluidized beds is bed agglomeration, which, in the worst case, may result in total defluidization of the bed and unscheduled downtime. Because of the special ash-forming constituents of biomass fuels, several of these fuels have been shown to be especially problematic. Despite the frequent reporting, a precise and quantitative knowledge of the bed agglomeration process during fluidized bed combustion of biomass fuels has not yet been presented. Bed sampling versus operation time was performed in four different biomass-fired full-scale fluidized beds, as well as during controlled fluidized bed agglomeration tests in bench-scale testing of five representative biomass fuels. The bed materials and agglomerates were further analyzed using scanning electron microscopy, coupled with energy-dispersive spectroscopy SEM/EDS, to determine the characteristics of the formed bed particle layers. For typical wood fuels, coating-induced agglomeration with subsequent attack reaction and diffusion by calcium into the quartz was identified to be the dominating bed agglomeration mechanism. Low-melting calcium-based silicates (including minor amounts of, for example, potassium) were formed with subsequent viscous-flow sintering and agglomeration. For high-alkali-containing biomass fuels, direct attack of the quartz bed particle by potassium compounds in a gas or aerosol phase formed a layer of low-melting potassium silicate. Thus, formation and subsequent viscous-flow sintering and agglomeration seemed to be the dominating agglomeration mechanism for these fuels.