The combustion behavior and excess heat release during the oxy-fuel combustion of blended coals were investigated experimentally using a non-isothermal thermogravimetric analyzer. The atmospheres were set to 10%O2/90%CO2, 21%O2/79%N2, 30%O2/70%CO2, and 50%O2/50%CO2, and Arthur coal (bituminous coal, BA) and KPU (sub-bituminous coal, SK) were selected as fuel with blending ratios of BA25%/SK75%, BA50%/SK50%, and BA75%/SK25%. The purpose of this study is to investigate the interaction between the blended coals and the effects of blending ratio and oxygen concentration on the excess heat release under oxy-fuel combustion. The results showed that as the oxygen concentration and proportion of sub-bituminous coal increased, the peak value in the differential thermal analysis curve increased by the enhanced reaction rate. A higher oxygen concentration led to excess heat release. The ignition temperatures depended on the volatile matter content of the sub-bituminous coal, whereas the burnout temperature was largely affected by the fixed carbon content of the bituminous coal. For interaction behaviors on characteristic temperatures, the volatile release temperature shows an additive behavior; however, ignition and burnout temperatures show non-additive behaviors for blended coals.