Three promising biomass fuels for southern Mediterranean regions were tested for their agglomeration tendency in an atmospheric lab-scale fluidised bed (FB) gasifier using quartz and olivine as bed materials. The defluidisation temperatures of the energy crops Giant Reed (Arundo donax L.) and Sweet Sorghum bagasse were respectively approx. 790 °C and 810 °C, in both bed materials, while the agro industrial residue olive bagasse caused defluidisation of the quartz bed at 830 °C and olivine bed at > 850 °C. Agglomerates from these tests were analysed with SEM/EDS. Coatings and necks between bed particles were formed due to ash derived potassium silicate melt. For the first two fuels cluster-type agglomerates around remains of char particles were observed. Thermodynamic equilibrium simulations of each chemical system were performed to cross examine the predicted ash melting temperatures and chemistry with experimental findings. Predictions of potassium liquid compounds, like K2O·SiO2(l) were verified by EDS analyses on the particle coatings. FB gasification of olive bagasse resisted defluidisation up to higher temperatures because of its lower potassium and higher calcium content, especially in the case of olivine bed. The latter experimental finding coincided with thermodynamic predictions.