Membrane technology is considered an innovative and promising approach due to its flexibility and low energy consumption. In this work, a comprehensive 3D-CFD model of the Hollow-Fiber Membrane Contactor (HFMC) system for COsub.2 capture into aqueous MEA solution, considering a counter-current fluid flow, was developed and validated with experimental data. Two different flow arrangements were considered for the gas mixture and liquid solution inside the HFMC module. The simulation results showed that the COsub.2 absorption efficiency was considerably higher when the gas mixture was channeled through the membranes and the liquid phase flowed externally between the membranes, across a wide range of gas and liquid flow rates. Sensitivity studies were performed in order to determine the optimal COsub.2 capture process parameters under different operating conditions (flow rates/flow velocities and concentrations) and HFMC geometrical characteristics (e.g., porosity, diameter, and thickness of membranes). It was found that increasing the membrane radius, while maintaining a constant thickness, positively influenced the efficiency of COsub.2 absorption due to the higher mass transfer area and residence time. Conversely, higher membrane thickness resulted in higher mass transfer resistance. The optimal membrane thickness was also investigated for various inner fiber diameters, resulting in a thickness of 0.2 mm as optimal for a fiber inner radius of 0.225 mm. Additionally, a significant improvement in COsub.2 capture efficiency was observed when increasing membrane porosity to values below 0.2, at which point the increase dampened considerably. The best HFMC configuration involved a combination of low porosity, moderate thickness, and large fiber inner diameter, with gas flow occurring within the fiber membranes.