Hydrogenolytic ring cleavage of gem-difluorocyclopropanes occurs exclusively at the carbon-carbon bond opposite to the halogen-bearing center and affords mainly gem-difluoroalkanes. The intermediacy of catalyst/cyclopropane derived adducts (e.g., palladacyclobutanes or 1,3-dipalladiopropanes) is postulated in order to rationalize the formation of monofluorinated and halogen-free by-products and, in addition, to explain specific substituent effects on the reaction rates.