Bioenergy is considered as a sustainable energy which can play a significant role in the future’s energy scenarios to replace fossil fuels, not only in the heat production, but also in the electricity and transportation sectors. Emission formation and release of main ash-forming elements during thermal conversion of biomass fuels at different conditions have been the scope of this study. The experiments were conducted in a quartz glass reactor where the temperature and atmosphere could be controlled. The selected fuels represent a wide range of biomass compositions. They are torrefied softwood, spruce bark, waste wood, miscanthus, and wheat straw. The fuels were first grinded and then pressed with a pellet maker into pellets of the same size and weight. For each fuel, the experiments were carried out under both oxidation and pyrolysis condition, with atmosphere of 3 % O2 + 97 % N2 and 100 % N2, respectively, at four residence times. The selected temperatures under which experiments were performed are 800, 900, and 1,050 °C. The concentration of SO2, NO, CO, and CO2 emissions and O2 were monitored online by three analysers, simultaneously. The residue weight was measured after each process, and the comparison with the ash content of the fresh pellet is made. Additionally, the release of several ash-forming elements (K, Zn, Na, and Mn) from the fuels has been quantified as function of temperature and residence time by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). Time-dependent formation of NO and SO2 and other emissions is presented and discussed with respect to different temperature and combustion conditions.