A residential cereal burner (20 kW) was used to study the slagging characteristics of cereal grains with and without lime addition. The deposited bottom ash and slag were analyzed using X-ray diffraction (XRD), to identify the crystalline phases, and environmental scanning electron microscopy, coupled with energy-dispersive X-ray spectroscopy (ESEM/EDS), to study the morphology and elemental composition. Phase-diagram information was utilized to extract qualitative information about the behavior of cereal grain ashes under combustion conditions. Chemical equilibrium model calculations were used to interpret the experimental results. In addition, investigations of the melting behavior of the produced slags were conducted. The results showed significant differences in slagging characteristics between the fuels that were used. The slags consisted of high-temperature melting crystalline phases (calcium/magnesium potassium phosphates) and a potassium-rich phosphate melt for all cereal grains. For oat and barley, cristobalite was also identified in the slag. Furthermore, in these cases, the slags most probably contained a potassium-rich silica melt. The differences in the melting behaviors of the slags had a considerable effect on the performance of the burner. The addition of lime reduced the formation of slag for barley and totally eliminated it for rye and wheat. This occurs because lime contributes to the formation of high-temperature melting calcium potassium phosphates.