The present work mainly developed a mathematical model based on the plug flow model and coarse fly ash particles’ fragmentation model to describe the behavior and evolution of ash formation and the influence of the biomass feeding rate and flue gas cooling rate on ash properties, which is validated by literature data. The model considers homogeneous nucleation of alkali vapors, heterogeneous condensation of vapors on newly formed particles and fly ash particles, and collision-coagulation between aerosol particles, which is also applied to numerically study and analyze the ash formation characteristics in the cases of practical boiler pulverized fuel combustion and SO2 sulfation. The results show that the mathematical model can reasonably describe the ash formation and the influence of the biomass feeding rate and the flue gas cooling rate on the mass PSDs of PM10 and its elements. The initial nucleation temperature and initial nucleation particle size increase with the biomass feeding rate, which is of great importance to the cooling rate on the initial nucleation number concentration and the initial nucleation particle size. Elements Na, K, and Cl are mainly concentrated in PM1, but rarely distributed in PM1–10. The condensation of Na, K, and Cl on coarse particles increases with the biomass feeding rate and decreases with the cooling rate. The ash characteristics obtained from the experiment condition with an ultra-high flue gas cooling rate and minimum biomass selected may have a large deviation from that of practical biomass combustion, and the sulfated reaction may reduce Cl corrosion rather than ash deposition.