The objective of the present work was to find the accurate kinetic models and mechanism for CO2 absorption into tertiary amine solution, aiming at understanding the contribution of the CO2 reaction with H2O,OH-, and tertiary amines on the overall reaction rate. First, the kinetics of CO2 absorption into water instead of a buffer solution were studied using the stopped-flow technique at 293-313K, with initial CO2 molar concentration of 1.1-37.3 mM. The experimental first-order reaction rate constant (k0_CO2) was determined to be about 1000 times larger than the value for CO2 absorption into buffer solution reported in the reference. The k0_CO2 was then correlated by a proposed semiempirical model and a simplified theoretical model, giving the activation energy for CO2 reacting with H2O as fitted by the simplified theoretical model in good agreement with the value of previous research. Also, the pH values and hydroxyl ion concentrations of aqueous Diethylaminoethanol (DEEA) solutions were determined at 293-313K, with DEEA molar concentration of 0.1-0.4 M and CO2 loading of 0-0.626mol/mol. In addition, the observed first-order reaction rate constant (k(0_DEEA)) of binary DEEA-H2O solution with DEEA molar concentration of 0.1-0.4 M reacting with CO2 was determined at 293-313K. It should be pointed out that the kinetic experiments of CO2 absorption into DEEA solution was done with the molar ratio of DEEA to CO2 fixed at 20. The values ofk(0_DEEA) were then fitted and predicted by four models (i.e., termolecular model, base-catalyzed model, the improved model, and Khalifah model). The results show the improved model and Khalifah model can predictk(0_DEEA) well with an average absolute relative difference (AARD) <5%. The predicted results indicate that the contribution ofOH(-) tok(0_DEEA) cannot be ignored for the absorption of CO2 into tertiary amine solutions, and could be responsible for 50-70% of the total absorption reaction rate. Furthermore, thek(0) value of CO2 absorption into aqueous triethanolamine and CO2-loaded DEEA solution were further investigated and comprehensively discussed, suggesting that bothpK(a) and the CO2 solubility affectk(0), withpK(a) having a much more significant effect. (c) 2018 American Institute of Chemical Engineers AIChE J, 65: 652-661, 2019