In this study, the thermogravimetric analysis (TGA) method has been used to evaluate the kinetic behavior of biomass, coal and its blends during oxyfuel co-combustion. The thermogravimetric results have been evaluated by the Coats-Redfern method and validated by Criado's method. TG and DTG curves indicate that as the oxygen concentration increases the ignition and burn out temperatures approach a lower temperature region. The combustion characteristic index shows that biomass to coal blends of 28% and 40% respectively can achieve enhanced combustion up to 60% oxygen enrichment. In the devolatilization region, the activation energies for coal and blends reduce while in the char oxidation region, they increase with rise in oxygen concentration. Biomass, however, indicates slightly different combustion characteristic of being degraded in a single step and its activation energies increase with rise in oxygen concentration. It is demonstrated in this work that oxygen enrichment has more positive combustion effect on coal than biomass. At 20% oxygen enrichment, 28% and 40% blends indicate activation energy of 132.8 and 125.5 kJ . mol(-1) respectively which are lower than coal at 148.1 kJ . mol(-1) but higher than biomass at 81.5 kJ . mol(-1) demonstrating synergistic effect of fuel blending. Also, at char combustion step, an increase in activation energy for 28% blend is found to be 0.36 kJ . mol(-1) per rise in oxygen concentration which is higher than in 40% blend at 0.28 kJ . mol(-1). (C) 2020 The Authors. The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.