The presence of inorganic elements in solid fuels is not only considered a direct source of problems in the furnace but is also connected with the release of pollutants into air during combustion. This article focuses on the sintering characteristics of biomass and coal ashes, in particular on the leaching processes, and their impact on the tendency to sinter ash. Biomass and coal ash with high alkali metal concentration can deposit in boiler sections and cause severe operating problems such as slagging, fouling and corrosion of boiler and heat exchanger surface, limiting heat transfer. Two biomass types and one coal ash with different origin and different chemical compositions were investigated. A sequential leaching analysis was employed in this study to elucidate the modes of occurrence of metals that can transform into fuel extract. Sequential leaching analysis was conducted as a two-step process: using distilled water in the first step and acetic acid in the second step. The chemical composition of ashes, before and after each step of the leaching processwas studied using ICP-OES method. The standard Ash Fusion Temperature (AFTs) technique was also employed to assess the sintering tendency of the tested samples. It was observed that the presence of key elements such as sodium, potassium, magnesium and sulphur (elucidated in the leaching process) plays a significant role in sintering process. The sintering tendency enhances when the concentration of these elements increases.