This work focused on the application of a microchannel contactor for CO2 capture using water as absorbent, especially for the application of CO2-rich gas. The influence of operating conditions (temperature, volumetric flow rate of gas and liquid, and CO2 concentration) on the absorption efficiency and the overall liquid-side volumetric mass transfer coefficient was presented in terms of the main effects and interactions based on the factorial design of experiments. It was found that 70.9% of CO2 capture was achieved under the operating conditions as follows; temperature of 50 °C, CO2 inlet fraction of 53.7%, total gas volumetric flow rate of 150 mL min−1, and adsorbent volumetric flow rate of 1 mL min−1. Outstanding performance of CO2 capture was demonstrated with the overall liquid-side volumetric mass transfer coefficient of 0.26 s−1. Further enhancing the system by using 2.2 M of monoethanolamine in water (1:1 molar ratio of MEA-to-CO2) boosted the absorption efficiency up to 88%.