This study investigated CO2 capture from flue gas by using glycerol as solvent. Absorption was simulated using a rate-based model with three cases under similar operating conditions. CO2 separation was first simulated using ENRTL-RK thermodynamic model with monoethanolamine (MEA) as. solvent. CO2 absorption was then simulated using NRTL-RK thermodynamic model with glycerol solvent, and then an aqueous mixture of MEA/glycerol was also simulated using ENRTL-RK thermodynamic model. Simulation results confirm that glycerol can be used as promoter with MEA solvent to enhance CO2 capture. The optimal glycerol concentration for CO2 absorption is 10-40 wt %, in which 10 wt % glycerol exhibits the lowest CO2 concentration in the outlet gas from the absorber. The CO2 removal efficiency increases from 62.24% for 10 wt % MEA aqueous solution to 64.33% for the mixture of 10 wt % MEA-10 wt % glycerol aqueous solution. The CO2 removal efficiency for 10 wt % glycerol aqueous solution is 27.31%.