Solvent degradation represents one of the main operational drawbacks of the post-combustion CO2 capture process. Degradation not only induces additional costs for solvent make-up, it also impacts the process efficiency and its environmental penalty due to the emission of various degradation products. There is still a gap of knowledge about the influence of process operating conditions on degradation, making it currently impossible to predict the solvent degradation rate in CO2 capture plants. Morever, the reaction mechanisms corresponding to solvent degradation are very slow, significantly complicating its study in industrial units. In the present work, appropriate experimental equipment and analytical methods are developed for accelerating the degradation of monoethanolamine solvents (MEA). The relevance of accelerated conditions is established by comparing artificially degraded solvent samples with degraded solvent samples from industrial CO2 capture pilot plants. Two approaches are evaluated implying either discontinuous or continuous gas feed, this latest being the most representative of industrial degradation. The respective influences of the gas feed composition and the gas-liquid transfer are evidenced and quantified. Finally, the present study leads to a better understanding of solvent degradation in the CO2 capture process with MEA. More generally, it also evidences that accelerated conditions at laboratory-scale may provide relevant information for the study of slow phenomena taking place in large-scale industrial processes. Further works include the development of a kinetic model for MEA solvent degradation and the extension of this methodology to other promising solvents in order to facilitate the operation and large-scale deployment of CO2 capture.