The presented work is focused on biomass thermochemical conversion with integrated CO2 capture. The main aim of this study was the in-depth investigation of the impact of pyrolysis temperature (500, 600 and 700 °C) and CaO sorbent addition on the chemical and physical properties of obtained char and syngas. Under the effect of the pyrolysis temperature, the properties of biomass chars were gradually changed, and this was confirmed by examination using thermal analysis, scanning electron microscopy, X-ray diffraction, and porosimetry methods. The chars were characterised by a noticeable carbon content (two times at 700 °C) resulting in a lower O/C ratio. The calculated combustion indexes indicated the better combustible properties of chars. In addition, structural morphology changes were observed. However, the increasing pyrolysis temperature resulted in changes of solid products; the differences of char properties were not significant in the range of 500 to 700 °C. Syngas was analysed using a gas chromatograph. The following main components were identified: CO, CO2, CH4, H2 and C2H4, C2H6, C3H6, C3H8. A significant impact of CaO on CO2 adsorption was found. The concentration of CO2 in syngas decreased with increased temperature, and the highest decrease occurred in the presence of CaO from above 60% to below 30% at 600 °C.