Nowadays, almost all countries in the world are intensifying their search for locally available energy sources to become independent of external supplies. The production of alternative fuels from biomass and waste by thermal treatment or direct use in the combustion process is still the simplest method for fast and cheap heat production. However, the different characteristics of these fuels can cause problems in the operation of the plants, resulting in increased air pollution. Therefore, the analysis of the thermal treatment of solid fuels is still an important issue from a practical point of view. This work aimed to study biomass combustion in a small-scale reactor using the in-house Extended DEM (XDEM) method based on mixed Lagrangian–Eulerian approaches. This was provided by a novel, independently developed coupling computational interface. This interface allows for a seamless integration between CFD and DEM, improving computational efficiency and accuracy. In addition, significant advances have been made in the underlying physical models. Within the DEM framework, each particle undergoes the thermochemical processes, allowing for the prediction of its shape and structural changes during heating. Together, these changes contribute to a more robust and reliable simulation tool capable of providing detailed insights into complex multi-phase flows and granular material behavior. Numerical results were obtained for a non-typical geometry to check the influence of the walls on the distribution of the parameters in the reactor. The results show that XDEM is a very good tool for predicting the phenomena during the thermal treatment of solid fuels. In particular, it provides information about all the moving particles undergoing chemical reactions, which is very difficult to obtain from measurements.