Abstract: In recent years, the continuous consumption of industrial fossil fuels has led to a rapid increase in CO₂ emissions, which has become a primary driver for exacerbating the greenhouse effect and global climate change. Reducing carbon emissions has thus emerged as an urgent challenge that needs to be addressed. Chemical absorption using aqueous alkanolamine solutions, represented by monoethanolamine, is regarded as one of the key post-combustion CO₂ capture technologies due to its excellent CO₂ absorption performance and high technical maturity. However, its large-scale application is severely restricted by issues such as high energy consumption during solvent regeneration and significant solvent loss caused by volatility and degradation at high temperatures. Catalytic desorption technology introduces solid acid catalysts into CO₂-rich absorbents, lowering the activation energy of the CO₂ desorption process by accelerating proton transfer and promoting C—N bond cleavage. This approach enhances CO₂ desorption efficiency and reduces the required desorption temperature, thereby decreasing both the sensible and latent heat needed for solvent regeneration. As a result, it not only achieves substantial reductions in regeneration energy consumption but also minimizes solvent evaporation and loss, demonstrating enormous application potential and becoming a research focus worldwide. This paper systematically reviews advances in solid acid catalysts for CO₂ catalytic desorption over the past five years, focusing on the types and characteristics of these catalysts, the relationships between catalyst structure and desorption performance, and the mechanisms underlying the enhancement of CO₂ desorption. It deeply explores the synergistic effects and reaction pathways of Lewis acid sites, Brønsted acid sites, and basic sites in different catalysts during the CO₂ catalytic desorption process. Finally, the paper identifies critical scientific challenges in current research and proposes future directions for CO₂ catalytic desorption, aiming to provide fundamental and theoretical support for technological development and promote its industrial application in large-scale, low-cost carbon capture.