Adsorption equilibria of a CO2/H2O binary mixture on activated alumina F-200 were measured at several temperatures and over a wide range of concentrations from 4% to around 90% of the saturated water vapor pressure. In comparison with the single-component data, the loading of CO2 was not reduced in the presence of H2O, whereas at low relative humidity the adsorption of H2O was depressed. The binary system was described by a competitive/cooperative adsorption model where the readily adsorbed water layers acted as secondary sites for further CO2 adsorption via hydrogen bonding or hydration reaction. The combination of kinetic models, namely, a Langmuir isotherm for characterizing pure CO2 adsorption and a BET isotherm for H2O, was extended to derive a binary adsorption equilibrium model for the CO2/H2O mixture. Models based on the ideal adsorbed solution theory of Myers and Prausnitz failed to characterize the data over the whole composition range, and a large deviation of binary CO2/H2O equilibrium from ideal solution behavior was observed. The extended Langmuir-BET (LBET) isotherm, analogous to the extended Langmuir equation, drastically underestimated the CO2 loading. By incorporating the interactions between CO2 and H2O molecules on the adsorbent surface and taking into account the effect of nonideality, the realistic interactive LBET (R-LBET) model was found to be in very good agreement with the experimental data. The derived binary isosteric heat of adsorption showed that the heat was reduced by competitive adsorption but promoted by cooperative adsorption.