Biomass fuels with calcium and potassium as the main ash-forming elements are expected to form ash consisting mainly of carbonates and oxides. These carbonates are stable in a rather narrow temperature range, which in turn depends on the Ca/K ratio, as well as on the surrounding atmosphere. The objective of the present study was to perform a detailed characterization of ash formation and transformation at a single-pellet level during combustion of silicon-poor woody biomass fuel. Combustion tests were performed with poplar in a single-pellet isothermal thermogravimetric analyzer operated at different temperatures and atmospheres and quenched at different stages of fuel conversion. The char and residual ashes were characterized for morphology and chemical composition. The focus of the experimental work in this study was on the time (conversion) resolved ash formation and transformations at the late part of the char combustion phase. Thermodynamic equilibrium calculations were used both to design the experiments and to support the interpretation of experimental results. It was concluded that carbonates were, in general, stable at low temperatures (here, 600–800 °C), identified as CaCO3, K2Ca2(CO3)3, and K2Ca(CO3)2, and decomposed at higher temperatures. In addition, a combined carbonate and phosphate phase in the form of carbonate apatite, Ca9.9(PO4)6(CO3)0.9, was also found, mainly at lower temperatures. However, for char/ash samples quenched before full conversion, CaCO3 was still found at temperatures higher than expected, possibly explained by the stabilizing effect of locally higher CO2 partial pressure within the burning fuel particles. Thus, the results of the present study provide new insights into conversion-based ash formation and transformation in a burning fuel particle with relevance for combustion of Si-poor woody biomass fuels.