The aim of this work was to study the role of SO2 in non-aqueous solution of blended monoethylethanolamine (EMEA) and diethylethanolamine (DEEA) for CO2 capture. The CO2-loaded EMEA + DEEA solution (0.4 mol of CO2/mol of EMEA) was degraded with 0.015 m(3) h(-1) mixed gas (200 ppm of SO2 balanced with N-2) at 333.15 K for 10 days. The reaction of SO2 with the CO2-loaded EMEA + DEEA solution was explored using the H-1 and C-13 nuclear magnetic resonance, electrospray ionization mass spectrometry, and elemental analysis methods. The results revealed that SO2 can be absorbed immediately and accumulated in the solution. SO2 can react with amino and hydroxyl in EMEA and hydroxyl in DEEA and carbamate, directly forming organic sulfide, which can be further degraded. Additionally, the CO2-SO2-loaded EMEA + DEEA solution can be purified using ion-exchange resins to remove heat-stable salts.