The ash behavior during suspension firing of 12 alternative solid biofuels, such as pectin waste, mash from a beer brewery, or waste from cigarette production have been studied and compared to wood and straw ash behavior. Laboratory suspension firing tests were performed on an entrained flow reactor and a swirl burner test rig, with special emphasis on the formation of fly ash and ash deposit. Thermodynamic equilibrium calculations were performed to support the interpretation of the experiments. To generalize the results of the combustion tests, the fuels are classified according to fuel ash analysis into three main groups depending upon their ash content of silica, alkali metal, and calcium and magnesium. To further detail the biomass classification, the relative molar ratio of Cl, S, and P to alkali were included. The study has led to knowledge on biomass fuel ash composition influence on ash transformation, ash deposit flux, and deposit chlorine content when biomass fuels are applied for suspension combustion.