This study employs non-thermal Computational Fluid Dynamics (CFD) simulations to explore the efficacy of a gas–liquid vortex reactor (GLVR) for intensifying CO2 capture. The investigation concentrates on the multiphase flow and mass transfer behavior in diverse GLVR experimental units. Employing a multiphase Euler-Euler CFD model integrated with a Population Balance Model (CFD-PBM), a mass transfer model, and reaction kinetics, allows us to accurately simulate the reactive absorption of CO2 into aqueous Monoethanolamine (MEA). Experiments are conducted using a 30 wt% MEA solution for CO2 absorption, serving the purpose of model validation. This comprehensive approach enables a simulation of complex dynamics within the GLVR, emphasizing bubble breakage, coalescence, and reactive mass transfer processes. Examining bubble size distribution, pressure drop, CO2 absorption efficiency, and energy input systematically across various reactor geometries and operational conditions, our findings demonstrate that an optimized GLVR configuration significantly enhances CO2 absorption compared to the original design. Furthermore, the optimized GLVR outperforms state-of-the-art process intensification equipment in terms of CO2 absorption rate per unit reactor volume and energy efficiency.