One of the main barriers for the successful utilization of new biomass feedstocks.in commercial pellet boilers is the lack of knowledge about the combustion behavior of such fuels, particularly in terms of ash slagging, which can potentially damage the boiler and limit combustion efficiency. The VI Framework European project Domoheat studied the combustion of 15 Mediterranean woody and herbaceous biomass fuels in commercial 60 kW domestic pellet boilers. The performance of several methods for the prediction of measured boiler slagging was tested, including ash composition-based slagging indices, standard ash initial deformation temperature (IDT), and a new slagging laboratory method, the BioSlag test, based on the sieving of the ash and slag obtained in the combustion of 250 g of fuel in a furnace at controlled temperature conditions. IDT values allowed us to identify slagging in fuels with high silica (e.g., rye straw.pellet) or alkali contents (e.g., almond shell) but failed to discriminate medium slagging of fuels such as contaminated poplar chip. Slagging indices based on silica and alkali content of the ashes showed success for predicting boiler-observed slagging. The BioSlag test predicted observed slagging percentage in the boiler with R-2 = 0.87. This test could discriminate both high slagging of fuels with high Si content (e.g., rye straw pellet, pinecone seed shell) and the medium slagging tendency caused by alkali elements (e.g., almond shell, olive stone) and by moderate Si contents (e.g., contaminated poplar chip).