In this work, a comprehensive mathematical model was developed in order to evaluate the CO2 capture process in a microporous polypropylene hollow-fiber membrane countercurrent contactor, using monoethanolamine (MEA) as the chemical solvent. In terms of CO2 chemical absorption, the developed model showed excellent agreement with the experimental data published in the literature for a wide range of operating conditions (R2 > 0.96), 1−2.7 L/min gas flow rates and 10−30 L/h liquid flow rates. Based on developed model, the effects of the gas flow rate, aqueous liquid absorbents’ flow rate and also inlet CO2 concentration on the removal efficiency of CO2 were determined. The % removal of CO2 increased while increasing the MEA solution flow rate; 81% of CO2 was removed at the high flow rate. The CO2 removal efficiency decreased while increasing the gas flow rate, and the residence time in the hollow-fiber membrane contactors increased when the gas flow rate was lower, reaching 97% at a gas flow rate of 1 L‧min−1. However, the effect was more pronounced while operating at high gas flow rates. Additionally, the influence of momentous operational parameters such as the number of fibers and module length on the CO2 separation efficiency was evaluated. On this basis, the developed model was also used to evaluate CO2 capture process in hollow-fiber membrane contactors in a flexible operation scenario (with variation in operating conditions) in order to predict the process parameters (liquid and gaseous flows, composition of the streams, mass transfer area, mass transfer coefficient, etc.).