In the present paper, we investigated CO2 capture with 24 tertiary amine absorbents, including three synthetic amines, with systematic modification of their chemical structures. Aqueous solutions of the amines (mass fraction 30%) were used to evaluate the performance for CO2 capture. Gas scrubbing, vapor-liquid equilibrium (VLE), and reaction calorimetry experiments were conducted in the laboratory to obtain the absorption rate, the amount of CO2 absorbed, cyclic CO2 capacity, and heat of reaction for each absorbent. The results for these absorbents were compared with the conventional tertiary absorbent N-methyldiethanolamine (MDEA). Seven of the investigated absorbents performed well with high absorption rates and cyclic capacities. Among these absorbents, some showed lower heats of reaction than MDEA. These results provide basic guidelines for discovery of potential tertiary amine-based absorbents that may lead to development of new absorbent systems in the CO2 capture area.