The enthalpies of solution, HS, of carbon dioxide in aqueous methyldiethanolamine were measured with an isothermal flow calorimeter over wide ranges of temperature, pressure, weight percent MDEA, and loading (gmole CO2/gmole MDEA). The values of HS (kJ/gmole CO2) were found to be constant up to the saturation concentration of CO2 in the aqueous solution. In addition, experimental data showed that HS was independent of the total pressure over the solution, but linearly dependent upon both temperature and weight percent MDEA as was given by a correlation. A computer program based upon basic thermodynamic quantities was developed to model HS of CO2 in MDEA solutions. The values of K and ΔH for each of the chemical reactions (except the MDEA protonation reaction) were fitted values from the literature. Activity coefficient correlations used in the program were also obtained from the literature. Using these data, the program was first used to find the values of K and ΔH for the MDEA protonation reaction which gave the minimum error between the model and the experimental data. Finally, the values of HS predicted by the program were compared to the experimental data and the differences were discussed.