The Paris Agreement and one of its goals, “carbon neutrality,” require intensive studies on CO₂ absorption and desorption processes. When searching for ways of reducing the huge energy cost of CO₂ desorption in the amine scrubbing process, the combination of blended amine with solid acid catalysts turned out to be a powerful solution in need of further investigation. In this study, the tri-solvent MEA (monoethanolamine) + EAE(2-(ethylamino)ethanol) + AMP(2-amino-2-methyl-1-propanol) was prepared at: 0.2 + 2 + 2, 0.5 + 2 + 2, 0.3 + 1.5 + 2.5 and 0.2 + 1 + 3 mol/L. The heterogeneous catalytic CO₂ desorptions were tested with five commercial catalysts: blended γ-Al₂O₃/H-ZSM-5, H-beta, H-mordenite, HND-8 and HND-580. Desorption experiments were conducted via a recirculation process with direct heating at 363 K or using temperature programming method having a range of 303–363 K. Then, the average CO₂ desorption rate, heat duty and desorption factors were studied. After comparison, the order of CO₂ desorption performance was found to be HND-8 > HND-580 > H-mordenite > Hβ > blended γ-Al₂O₃/H-ZSM-5 > no catalyst. Among the other combinations, the 0.2 + 1 + 3 mol/L MEA + EAE + AMP with HND-8 had a minimized heat duty (HD) of 589.3 kJ/mol CO₂ and the biggest desorption factor (DF) of 0.0277 × (10⁻³ mol CO₂)³/L² kJ min. This study provided a kind of tri-solvent with catalysts as an energy-efficient solution for CO₂ absorption and desorption in industrial CO₂ capture pilot plants.