Fluorinated organic compounds are ubiquitous in pharmaceuticals and agrochemicals because they typically exhibit improved lipophilicity, binding affinity, and metabolic stability relative to their non-fluorinated counterparts. Despite their significance, selective and efficient fluorovinylation and fluoroalkylation protocols remain underdeveloped. Fluorinated commodity chemicals such as vinylidene fluoride (VDF), trifluoropropene (TFP), hexafluoropropene (HFP), and trifluoromethyl iodide (TFMI) represent intuitive fluorovinylation and fluoroalkylation reagents. However, their gaseous nature at room temperature and pressure (RTP) limits their practical use. We report that fluorinated gases can be stored within a magnesium-based metal–organic framework (MOF), enabling their handling as solid reagents for the first time. Encapsulation of the gas–MOF reagents within wax facilitates their stable storage in air at RT for up to two months without any loss in performance. Employing these gas–MOF reagents, we discovered that VDF undergoes Pd-catalyzed defluorinative couplings with (hetero)arylboronic acids to yield α-fluorostyrenes. Alternatively, the gem-difluorovinylated analogues can be accessed by converting VDF to a 2,2-difluorovinylzinc chloride intermediate that engages in Negishi couplings with (hetero)aryl halides to deliver β,β-difluorostyrenes. Furthermore, we uncovered a defluorinative coupling of VDF with NH-heteroarenes, producing novel N-fluorovinylated heterocycles. Demonstrating the generality of this delivery strategy to other gaseous reagents, TFP participates in Heck couplings with aryl halides to furnish β-trifluoromethylstyrenes, while TFMI undergoes Fe-catalyzed oxidative trifluoromethylations of (hetero)arenes. Given the successful delivery of a range of fluorinated gases using MOFs, this strategy provides a generalizable and user-friendly platform for discovering new reactions involving (fluorinated) gaseous reagents.