Deep eutectic solvents (DESs) cannot absorb SO2 at high temperatures, due to the lower solubility of the toxic gas in DESs at high temperatures, limiting their wider uptake in industrial applications. To address this knowledge gap, we added Na2S to a series of DESs to improve SO2 adsorption capacity at elevated operating temperatures in this work. The experimental results show that the newly designed Na2S-EG-MTPB DESs can adsorb SO2 effectively up to 90 °C. Solid products resulted from the interaction of SO2 and Na2S-EG-MTPB DES is mainly elemental sulfur (S8) and sodium sulfite (Na2SO3). DESs can be reused for SO2 absorption for at least five times by adding additional Na2S. Therefore, Na2S-EG-MTPB DESs have great potential as substitutes for existing SO2 absorbents due to their excellent high temperature resistance, high SO2 absorption capacity and low cost.