Abstract Two mesoporous fluorinated metal–organic frameworks (MOFs) were synthesized from extensively fluorinated tritopic carboxylate‐ and tetrazolate‐based ligands. The tetrazolate‐based framework MOFF‐5 has an accessible surface area of 2445 m 2 g −1 , the highest among fluorinated MOFs. Crystals of MOFF‐5 adsorb hydrocarbons, fluorocarbons, and chlorofluorocarbons (CFCs)—the latter two being ozone‐depleting substances and potent greenhouse species—with weight capacities of up to 225 %. The material exhibits an apparent preference for the adsorption of non‐spherical molecules, binding unusually low amounts of both tetrafluoromethane and sulfur hexafluoride.