Carbon Capture and Storage (CCS) is one of the main options for carbon dioxide mitigation. Capture processes based on CO2 dissolution in alkanolamine solutions are considered among the most adequate methods for decarbonation of post-combustion effluents [1]. An understanding of molecular interactions involved in {CO2 + water + alkanolamine} systems is essential to optimize gas absorbents and reduce process costs. The aim of this work is to compare thermodynamic properties of {alkanolamine + water} mixtures obtained experimentally and from molecular simulations. Molecular simulation provides a detailed microscopic view into thermodynamics and transport properties and is complementary to experimental measurements. Simulation is also a promising tool for the prediction of properties required to design capture process. The insights into microscopic structure and energetics of {alkanolamine + water} mixtures obtained from simulation, such as differences in hydrogen-bond interactions between different alkanolamines, contribute to improve structure-property relationships. A force field adapted to describe alkanolamines containing the N-C-C-O backbone was developed [2], taking into account the polar solvation environment. This new force field was validated through prediction of enthalpic and volumetric properties of seven alkanolamines, which are methyl- and ethyl-substituted monoethanolamine (MEA). The force field was then used to calculate the enthalpy of mixing of alkanolamines with water. The interaction between amine and water was modified adding a specific Lennard-Jones site in order to reproduce enthalpies of mixing of two {alkanolamine + water} systems. This model was then used to predict mixing properties for other systems. Simulation results are compared to experimental data obtained from mixing calorimetry using both flow mixing and titration techniques. The agreement observed was good and allowed the study of structural quantities, hydrogen bonding, cluster analysis, etc. The dependence of enthalpy of mixing with temperature was also investigated and comparison between experimental values and simulation is reported.