Deposits formation on heat transfer surfaces is one of the main problems associated to biomass co-combustion. It reduces plant efficiency and availability and increases maintenance costs. It is obvious that an increasing amount of low-temperature melting components in fuel ash accelerates and aggravates this process. Research is done to evaluate the validity of thermal analysis methods to characterise fusion of biomass and waste ashes. Laboratory ashes from a set of biomass and waste fuels are leached in successive steps. The original and the leached ashes are analysed by Thermo-Mechanical Analysis (TMA). Traces obtained from TMA show to be promising ash fingerprints to classify deposition tendencies. Additionally Simultaneous Thermal Analysis (STA) is performed on selected samples. Furthermore, improved chemical equilibrium calculations are proposed to predict the proportion of melted species resulting from combustion of biomass fuels. The model takes into account the reactivity of the inorganic matter in the fuel as issued from ash leaching.