Our quest for made-to-order materials that can address efficiently the separation and capture of CO2 at different concentrations has prompted us to explore the potential of various fluorinated MOFs with different structural properties and chemical compositions. Indeed, the successful practice of reticular chemistry allowed us to fabricate a series of isoreticular fluorinated MOFs with periodically arrayed hexafluorosilicate (SIFSIX) pillars, called SIFSIX-3-Zn, SIFSIX-3-Cu and SIFSIX-3-Ni. These aforementioned porous MOFs disclose unique features for carbon capture, namely uniformly aligned strong CO2 adsorption sites in an idealized and contracted pore system with high localized charge density. Particularly the use of a relatively small cation, i.e. Cu2+, led to an isoreticular analogue with a very high selectivity toward CO2 adsorption at very low CO2 partial pressures when compared to other physical adsorbents reported in the open literature.