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We report a novel Fe(II) compartmentalized coordination polymer (CCP) capable of physisorbing gas molecules in a selective manner. The crystal structure was modelled theoretically under the Density Functional Theory revealing the presence of discrete voids of 380 Å3, significantly larger than those reported for its predecesors. Adsorption isotherms of pure N2, CH4 and CO2 were measured, obtaining a loading capacity of 0.6, 1.7 and 2.2 molecules/void at 10 bar and at 298 K. Dynamic breakthrough gas experiments have been performed at different fluxes and temperatures, showing efficient adsorption and excellent selectivities for CO2 in gas mixtures with methane and nitrogen.