Display omitted •A series of novel GlyK/DMF/H2O solvents was successfully developed for CO2 capture.•NMR spectroscopy was used to identify the species at different phases.•The upper liquid phase of developed solvent was free from CO2-containing species.•The heat duty of solvent was reduced by 59.1% compared to the aqueous solvent. The energy penalty is a primary limitation for the implementation of the aqueous solvents for large-scale post-combustion CO2 capture processes. In this study, a novel aqueous-based phase change solvent, composed of potassium glycinate (GlyK, reactive species), water (H2O, solvent) and dimethylformamide (DMF, antisolvent) was developed to improve the energy efficiency of CO2 capture. To examine the role of the antisolvent, a series of aqueous-based amino acid solvents (GlyK-X) with different DMF:H2O (X) volume ratios was prepared, fully characterized and assessed. It was observed that a CO2-free phase appeared at the top of the aqueous-based amino acid GlyK-X solvents after CO2 absorption which can be easily separated and recycled to the absorption column and save energy. The results showed that the GlyK-60 solvent with DMF:H2O volume ratio of 60:40 had a very high CO2-free phase volume (63%). Moreover, the GlyK-60 solvent exhibited 26.1% (0.433–0.546 mol CO2/mol GlyK) enhancement in CO2 absorption capacity, 38.5% (130–80 min) decrease in regeneration time and 59.1% reduction in relative heat duty compared to the conventional aqueous GlyK solvent. Overall, the outcomes confirmed that the aqueous-based phase change GlyK-60 solvent is a viable solvent option for large-scale CO2 capture with extra-low energy consumption and a key to the success of Paris Climate Accord.