Metal organic frameworks are frequently examined as potential solutions to complex gas phase separations problems. In many cases, the gas phase adsorption properties of these materials are quantified using single component gas adsorption isotherms and breakthrough experiments. In adsorption separations, however, it is common that the adsorbent participates in a multicomponent adsorption event. In the literature there is a general absence of multicomponent adsorption data with most data predicted via the Ideal Adsorbed Solution Theory or molecular simulations. Therefore, in this work, binary adsorption data of CO ₂ and water on UiO-66 were measured experimentally using a volumetric method at three different water loadings. Molecular simulations of isotherms were compared to the experimental measurements and the impact of two different MOF defect sites on the multicomponent CO ₂ /H ₂ O adsorption behavior was determined. The experimental data show a slight enhancement of CO ₂ loading when CO ₂ is co-adsorbed with water, which is a result that was confirmed via molecular simulations. Also, the simulation results show that defect sites can have a greater influence on low-pressure CO ₂ adsorption in MOFs than the co-adsorption of water. Furthermore, the simulations provide a molecular-level understanding of the role of these defects on the single and binary adsorption behavior.