Steam-fluidized bed gasification of biomass, which produces combustible gases from which transportation fuels can be synthesized, is a promising option for replacing the use of fossil fuels in the transportation sector. Similar to other thermal conversion processes, the release of potassium (K), chlorine (Cl), and sulfur (S) from biomass fuels to the gas phase during this process may be conducive to ash-related problems. Catalytic tar and char conversion by K has also been observed. In addition to operational conditions, the extent to which these elements are released to the gas phase may be affected by fuel ash characteristics such as the ash composition and the speciation (or association) of ash-forming elements in the fuel matrix. In the present work, the influence of these fuel ash characteristics on the extent to which K, Cl, and S are released from biomass fuels to the gas phase was studied under steam-fluidized bed gasification. The aim was to assess whether these fuel ash characteristics provide information that could be useful in making a quick judgment as to what extent K, Cl, and S would be released to the gas phase. To this end, the release of K, Cl, and S from forest residues and wheat straw during devolatilization and steam gasification of the char was quantified in a laboratory-scale bubbling fluidized bed reactor. The speciation of these elements in the virgin fuels was studied with chemical fractionation. The results reveal that the extent to which S is released from biomass fuels to the gas phase mainly depends on its speciation in the fuel matrix. While both the ash composition (mainly the Cl/K molar ratio) of the fuel and the speciation of K in the fuel matrix are relevant for the release of K, they appear to be unimportant with respect to the release of Cl.