The increasing demand for biomass fuels leads to the introduction of new biomass fuels into the market. These new biomass fuels (e.g., wastes and residues from agriculture and the food industry, short rotation coppices, and energy crops) are usually not well-defined regarding their combustion behavior. Therefore, fuel characterization methods with a special focus on combustion-related problems (gaseous NOx, HCl, and SOx emissions, ash-melting behavior, and PM emissions) have to be developed. For this purpose, fuel indexes are an interesting option. Fuel indexes are derived from chemical fuel analyses and are checked and evaluated regarding their applicability by measurements performed at lab- and real-scale combustion plants for a large variety of fuels. They provide the possibilities for a pre-evaluation of combustion-relevant problems that may arise from the use of a new biomass fuel. A possible relation to describe the corrosion risk is, for instance, the molar 2S/Cl ratio. The N content in the fuel is an indicator for NOx emissions, and the sum of the concentrations of K, Na, Zn, and Pb in the fuel can give a prediction of the aerosol emissions, whereas the molar (K + Na)/[x(2S + Cl)] ratio provides a first indication regarding the potential for gaseous HCl and SOx emissions. The molar Si/K ratio can supply information about the K release from the fuel to the gas phase. The molar Si/(Ca + Mg) ratio can give indications regarding the ash-melting temperatures for P-poor fuels. For P-rich fuels, the (Si + P + K)/(Ca + Mg) ratio can be used for the same purpose. The fuel indexes mentioned can provide a first pre-evaluation of combustion-relevant properties of biomass fuels. Therefore, time-consuming and expensive combustion tests can partly be saved. The indexes mentioned are especially developed for grate combustion plants, because interactions of the bed material possible in fluidized-bed combustion systems are not considered.