The most mature CO2 capture technology is absorption of monoethanolamine (MEA) in packed or spray columns. Typically, an aqueous 30 wt.% MEA solution is used. High MEA concentrations are believed to hinder mass transfer rate due to high viscosity of MEA. We worked, for the first time, on the effects of using pure MEA on overall mass transfer coefficient (KGɑ) and absorption efficiency in a spray column by varying several operational parameters. Image analysis results suggested that interfacial area increased with increasing liquid flow rate. As a result, KGɑ increased. As opposed the belief in literature, KGɑ also increased with increasing MEA concentrations. The highest KGɑ was obtained in this work (11.7 kmol·m−³∙kPa−1∙h−1) is around one order of magnitude higher than most literature studies. Having more MEA molecules on the surface of the droplets led to higher KGɑ. In addition, it was shown that absorption efficiency was largely determined by inlet CO2 to MEA molar ratio. 13C NMR spectra results revealed that similar levels of carbamate were formed for MEA concentrations up to 70 wt.%. A simplified analysis on regeneration heat duty showed that decreasing water amount can lead to 3–10 fold decrease in reboiler energy duty.