In this work, the composite catalysts, SO42/ZrO2/γ‐Al2O3 (SZA), with different ZrO2 and γ‐Al2O3 mass ratios were prepared and used for the first time for the carbon dioxide (CO2)‐loaded monoethanolamine (MEA) solvent regeneration process to reduce the heat duty. The regeneration characteristics with five catalysts (three SZA catalysts and two parent catalysts) of a 5 M MEA solution with an initial CO2 loading of 0.5 mol CO2/mol amine at 98°C were investigated in terms of CO2 desorption performance and compared with those of a blank test. All the catalysts were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, N2 adsorption–desorption experiment, ammonia temperature programmed desorption, and pyridine‐adsorption infrared spectroscopy. The results indicate that the SZA catalysts exhibited superior catalytic activity to the parent catalysts. A possible catalytic mechanism for the CO2 desorption process over SZA catalyst was proposed. The results reveal that SZA1/1, which possesses the highest joint value of Brφnsted acid sites (BASs) and mesopore surface area (MSA), presented the highest catalytic performance, decreasing the heat duty by 36.9% as compared to the catalyst‐free run. The SZA1/1 catalyst shows the best catalytic performance as compared with the reported catalyst for this purpose. Moreover, the SZA catalyst has advantages of low cost, good cyclic stability, easy regeneration and has no effect on the CO2 absorption performance of MEA. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3988–4001, 2018