In this study, the effects of wall thermal boundary conditions on the outer recirculation zone (ORZ) combustion modes transition in the DME/air swirling flames were investigated using the Large Eddy Simulation (LES) and Flamelet Generated Manifold (FGM) method. The results show that the ORZ chemistry and temperature are highly sensitive to the wall thermal boundary condition. Based on the correlation between the temperature and species observed in the time-averaged numerical results, the relation between the combustion mode and temperature in the ORZ was discovered. Through temporal analysis of species and heat release rate in the ORZ, the stable Mode II and Mode IV as well as the unstable Mode III were identified. The chemical reaction pathway analysis for typical probe in the ORZ reveals that different combustion modes undergo distinct (low-temperature or high-temperature) chemical reaction pathways. Afterwards, the definition of ORZ combustion modes used in experiments was refined by utilizing the chemical reaction data from the simulations. And it was applied to identify the combustion mode across the entire computational domain. The results confirm the consistency between the combustion modes determined in experiments based on OH and CH2O and those determined in simulations using chemical reaction rates. Finally, this explains the mechanism of the flickering flame in Mode III is the competition between the low-temperature and high-temperature reaction in the ORZ. Whereas the unstable Mode III can be stabilized by changing the wall temperature to reach the stable Mode II or Mode IV.