Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of 44 mmol g À 1 at a very low relative saturation pressure (P/P o ) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching 414 mmol g À 1 at P/P o of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane 4chlorodifluoromethane 4chlorotrifluoromethane 4tetrafluoromethane 4methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.