Simulations of CO2 and H2 sorption and separation were performed in [Cu(dpa)2SiF6-i], a metal-organic material (MOM) consisting of an interpenetrated square grid of Cu2+ ions coordinated to 4,4′-dipyridylacetylene (dpa) rings and pillars of SiF6 2- ions. This class of water stable MOMs shows great promise in practical gas sorption/separation with especially high selectivity for CO2 and variable selectivity for other energy related gases. Simulated CO2 sorption isotherms and isosteric heats of adsorption, Qst, at ambient temperatures were in excellent agreement with the experimental measurements at all pressures considered. Further, it was observed that the Qst for CO2 increases as a function of uptake in [Cu(dpa)2SiF6-i]. This suggests that nascently sorbed CO2 molecules within a channel contribute to a more energetically favorable site for additional CO2 molecules, i.e., in stark contrast to typical behavior, sorbate intermolecular interactions enhance sorption energetics with increased loading. The simulated structure at CO2 saturation shows a loading with tight packing of 8 CO2 molecules per unit cell. The CO2 molecules can be seen alternating between a vertical and horizontal alignment within a channel, with each CO2 molecule coordinating to an equatorial fluorine MOM atom. Calculated H 2 sorption isotherms and Qst values were also in good agreement with the experimental measurements in [Cu(dpa)2SiF 6-i]. H2 saturation corresponds to 10 H2 molecules per unit cell for the studied structure. Moreover, there were two observed binding sites for hydrogen sorption in [Cu(dpa)2SiF 6-i]. Simulations of a 30:70 CO2/H2 mixture, typical of syngas, in [Cu(dpa)2SiF6-i] showed that the MOM exhibited a high uptake and selectivity for CO2. In addition, it was observed that the presence of H2O had a negligible effect on the CO2 uptake and selectivity in [Cu(dpa)2SiF6-i], as simulations of a mixture containing CO2, H2, and small amounts of CO, N2, and H2O produced comparable results to the binary mixture simulations. © 2013 American Chemical Society.