The method of computational fluid dynamics (CFD) containing reactive mass transfer is adopted to simulate the process of carbon dioxide capture from flue gases with MEA in structured packing. The simulation of complex flows with second order reaction of CO₂ with MEA is built in representative elementary units (REU) of structured packed column. Various operating conditions including ratio of gas inlet flow to liquid inlet flow, CO₂ inlet mass fraction, MEA mole fraction and pressure on CO₂ capture process are examined. The absorption efficiency increases with the addition of MEA concentration and operating pressure, but decreases with CO₂ concentration and gas-liquid flow ratio. The influences of different factors on the absorption are ordered as MEA mole fraction, CO₂ mass fraction, ratio of gas inlet flow to liquid inlet flow and pressure. The CFD results of CO₂ absorption rate at different operating parameters are consistent with the reported ones, and the optimal parameters are got.