Three typical biomass fuels—rice husk, rice straw, and corn cobs—were combusted to understand the effects of ashing temperature on ash fouling and slagging characteristics. The ashes generated from combustion at 600 °C and 815 °C were characterized thoroughly with regard to their chemical composition. The systematic slagging/fouling indices of biomass were used to study the effects of ashing temperature on ash fouling and slagging propensities. The results showed that ashing temperature had a remarkable influence on ash composition, particle size distribution, ash morphology, ash fusibility, and thermal properties. Increased ashing temperature resulted in the expansion of ash particles together with the volatilization of alkali metals in the form of inorganic salts. Morphology analysis indicated that high ashing temperatures promoted biomass ash slagging. Ash fusion points increased at elevated ashing temperatures, while the ash content decreased. As a result of the volatilization and decomposition of biomass ash, a four-step mechanism of weight loss was clearly identified by thermal analysis. All prepared biomass ashes resulted in slagging and fouling problems at different levels during the thermo-chemical conversion of biomass.