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The ash behaviour comprises one major obstacle towards the efficient utilization of municipal solid wastes, (MSW), in incineration plants. The presence of large amounts of inorganic constituents such as alkali and alkali earth metals, chlorine, sulfur and zinc increase significantly the ash reactivity and lead to severe ash-related problems such as fouling, slagging, corrosion and erosion during their thermal treatment. In this paper, the melting behaviour of various ash fractions originating from the incineration of MSW is studied using simultaneous, (DSC/TG), thermal analysis methods. The produced results provide the basis for improved modelling of the ash behaviour during the incineration of MSW.