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CO 2 -binding organic liquids (CO 2 -BOLs) are switchable polarity solvents that can be used as nonaqueous green solvents for energy-efficient CO 2 capture. In this study, the novel three-component CO 2 -BOLs comprised of 1,1,3,3-tetramethylguanidine (TMG) as a superbase, an alkanol (methanol, nbutanol, sec-butanol, and 1-hexanol), and an amine (EEA, MEA, AMP, DEA, AEEA, PZ, TETA, and DETA) were introduced. Screening experiments were performed to find the best combination of solvent components based on CO 2 loading and absorption rate. The TMG/methanol/MEA BOL with a molar ratio of 0.3/0.6/0.1 was selected as the preferred solvent, which has an equilibrium absorption (α eq ) and a CO 2 uptake within 30 min (α R ) of 0.396 and 0.283 mol CO 2 /mol solvent, respectively. CO 2 -BOLs were characterized using FTIR, 1 H NMR, and 13 C NMR spectroscopy to specify the produced ionic species, explain the water inhibitory effect of MEA, and propose a plausible reaction mechanism for the reaction of CO 2 with the three-component BOLs in the absence and presence of water impurity. It was found that the addition of MEA to the two-component BOLs (base/alcohol) restricts the formation and precipitation of bicarbonate salt that leads to the lower energy consumption for solvent regeneration.