The {Cr8} metallacrown [CrF(O2CtBu)2]8, containing a F‐lined internal cavity, shows high selectivity for CO2 over N2. DFT calculations and absorption studies support the multiple binding of F‐groups to the C‐center of CO2 (C⋅⋅⋅F 3.190(9)–3.389(9) Å), as confirmed by single‐crystal X‐ray diffraction.