Is it possible to improve CO2 solubility in potassium carbonate (K2CO3)-based transition temperature mixtures (TTMs)? To assess this possibility, a ternary transition-temperature mixture (TTTM) was prepared by using a hindered amine, 2-amino-2-methyl-1,3-propanediol (AMPD). Fourier transform infrared spectroscopy (FT-IR) was employed to detect the functional groups including hydroxyl, amine, carbonate ion, and aliphatic functional groups in the prepared solvents. From thermogravimetric analysis (TGA), it was found that the addition of AMPD to the binary mixture can increase the thermal stability of TTTM. The viscosity findings showed that TTTM has a higher viscosity than TTM while their difference was decreased by increasing temperature. In addition, Eyring’s absolute rate theory was used to compute the activation parameters (∆G*, ∆H*, and ∆S*). The CO2 solubility in liquids was measured at a temperature of 303.15 K and pressures up to 1.8 MPa. The results disclosed that the CO2 solubility of TTTM was improved by the addition of AMPD. At the pressure of about 1.8 MPa, the CO2 mole fractions of TTM and TTTM were 0.1697 and 0.2022, respectively. To confirm the experimental data, density functional theory (DFT) was employed. From the DFT analysis, it was found that the TTTM + CO2 system has higher interaction energy (|∆E|) than the TTM + CO2 system indicating the higher CO2 affinity of the former system. This study might help scientists to better understand and to improve CO2 solubility in these types of solvents by choosing a suitable amine as HBD and finding the best combination of HBA and HBD.