Thermogravimetric analysis was employed to investigate the combustion characteristics of flax shives, beech wood, hemicellulose, cellulose, lignin, and their chars. The chars were prepared from raw materials in a fixed-bed reactor at 850 °C. In this study, the thermal behavior based on characteristic temperatures (ignition, maximum, and final temperatures), burnout time and maximum rate was investigated. The kinetic parameters for the combustion of different materials were determined based on the Coats-Redfern approach. The results of our study revealed that the combustion of pure pseudo-components behaved differently from that of biomass. Indeed, principal component analysis showed that the thermal behavior of both biomasses was generally similar to that of pure hemicellulose. However, pure cellulose and lignin showed different behaviors compared to flax shives, beech wood, and hemicellulose. Hemicellulose and cellulose chars had almost the same behaviors, while being different from biomass and lignin chars. Despite the difference between flax shives and beech wood, they showed almost the same thermal characteristics and apparent activation energies. Also, the combustion of the hemicellulose and cellulose chars showed that they have almost the same structure. Their overall thermal and kinetic behavior remained between that of biomass and lignin.