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The stabilities and hydrocarbon/fluorocarbon sorption properties of a zeolite-like metal-organic framework (MOF) Zn(hfipbb) with fluorinated channels has been studied. By the combination of thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements, we confirm that Zn(hfipbb) has exceptionally high hydrothermal and thermal stabilities. The adsorption behaviors of water and methanol by Zn(hfipbb) indicate that it is highly hydrophobic but with high adsorption of alcohols. Hexane and perfluorohexane adsorption measurements show that the fluorinated channels in Zn(hfipbb) have high affinity with hydrocarbon and fluorocarbon. The high fluorophilic nature of the channels and the high stability of the compound suggest its potential utility in practical separation applications.