The devolatilisation step of coal is a vital stage in both air-coal and oxy-coal combustion and there is interest in whether methods of estimating the reaction parameters are similar for both cases. A network pyrolysis model, the FG-DVC (Functional Group-Depolymerisation Vaporisation Cross-linking) code was employed to evaluate the effect of temperature (1273-1773K) and heating rate (104-106K/s) on the devolatilisation parameters of two coals of different rank. The products distribution between char and volatiles, and volatiles and NH3/HCN release kinetics were also determined. In order to assess the accuracy of the FG-DVC predictions, the values for nitrogen distribution and devolatilisation kinetics obtained for a temperature of 1273K and a heating rate of 105K/s were included as inputs in a Computational Fluid Dynamics (CFD) model for oxy-coal combustion in an entrained flow reactor (EFR). CFD simulations with the programme default devolatilisation kinetics were performed. The oxygen content in oxy-firing conditions ranged between 21% and 35%, and air-firing conditions were also employed as a reference. The experimental coals burnouts and oxygen concentrations from the EFR experiments were employed to test the accuracy of the CFD model. The temperature profiles, burning rates, char burnout and NO emissions during coal combustion in both air and O2/CO2 atmospheres were predicted. The predictions obtained when using the CFD model with FG-DVC coal devolatilisation kinetics were much closer to the experimental values than the predictions obtained with the ANSYS Fluent (version 12) program default kinetics. The predicted NO emissions under oxy-firing conditions were in good agreement with the experimental values.