Although separating CO2 from flue gas with ionic liquids has been regarded as a new and effective method, the mass transfer properties of CO2 absorption in these solvents have not been researched. In this paper, a coupled computational fluid dynamic (CFD) model and population balance model (PBM) was applied to study the mass transfer properties for capturing CO2 with ionic liquids solvents. The numerical simulation was performed using the Fluent code. Considering the unique properties of ionic liquids, the Eulerian-Eulerian two-flow model with a new drag coefficient correlation was employed for the gas-liquid fluid dynamic simulation. The gas holdup, interfacial area, and bubble size distribution in the bubble column reactor were predicted. The mass transfer coefficients were estimated with Higbie's penetration model. Furthermore, the velocity field and pressure field in the reactor were also predicted in this paper.