The goal of the current study was to investigate the influence of increased CO2 concentrations in oxy-fuel combustion on the products of coal devolatilization (gas, tar, soot and char). Experiments have been carried out in a laminar drop tube reactor (DTR) at conditions comparable to pulverized coal-fired boilers, in particular at a temperature of 1573 K and heating rate of 10(4)10(5) K/s. Atmospheres of N-2, Ar, and CO2 as well as with O-2/N-2 and O-2/CO2 mixtures (oxidizing oxy-fuel conditions) were applied. The work focuses on the early stages of reaction of coal particles in a pulverized combustor, therefore, a residence time of 120 ms was chosen, which assured the completion of pyrolysis while limiting the progress of char combustion and gasification. Gaseous, liquid and solid pyrolysis residues were extracted and analyzed by a multitude of techniques. A remarkable result is the effect that CO2 has on the solid products of pyrolysis. A much larger production of soot is observed in CO2 conditions over Ar or N-2 conditions (3:1). The combustion reactivity of both soot and char produced in CO2 is lower than that of the corresponding samples produced in Ar or N-2 atmosphere. Differences in reactivity couple with differences in the CO complexes residing on the surface and measured by XPS. The effect of CO2 on gaseous products is to increase the concentration of acetylene, while abating most other hydrocarbon species. When experiments are carried out in air and oxy-fuel atmospheres, soot and tar are consumed by combustion. Differences among chars are observed which can be mostly related to the attainment of different extents of burn out. In the oxy-fuel experiments, lower NO and NO2 and higher N2O concentrations are found in the gas compared to air experiments. (C) 2016 Elsevier B.V. All rights reserved.