In this study, an innovative approach for the selective absorption of carbon dioxide (CO2) by ionic liquid electrospray was proposed. First, the fluid dynamical characteristics of ionic liquid electrospray with 1-ethyl-3-methylimidazolium acetate in ambient air was clarified by highspeed imaging and aerosol analysis. This was followed by enhancement of CO2 absorption by ionic liquid electrospray in a closed chamber filled with CO2 which was successfully demonstrated for the first time. The ionic liquid electrospray drastically improves CO2 chemisorption by achieving higher CO2 loading ratio of ionic liquid due to the continuous generation of nano-sized droplets with a large specific surface area, as well as the sufficient spreading of the spray by the Coulomb repulsion between charged droplets.