Ash formation during thermochemical conversion of biomass-based pellets influences both char conversion rates and ash-related operational problems. The objective of the present study was to provide detailed insights into changes in fuel and ash properties during fuel conversion. Pellets of poplar wood and wheat straw were used as model biofuels, representing vastly different compositions of ash-forming elements. Pellet samples at different char conversion phases were analyzed by synchrotron-based 3D X-ray micro-tomography, to map and visualize the development of cracks, internal cavities, and ash layers during conversion. The analysis of ash layers was complemented by scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. The results provide new insights into how large cracks and internal cavities are developed already during devolatilization, for example, the poplar wood pellets had a 64% void fraction after the devolatilization stage. As expected, there were large variations between the ash layer properties for the two fuels. A porous, low density, and calcium-rich ash was formed from the poplar fuel, whereas the wheat straw ash was a high-density silicate melt that developed into bubbles on the surface. As the conversion proceeded, the wheat straw ash covered parts of the active char surface area, but without blocking the gas transport.