The radiation-induced addition reactions of ethers and alcohols to perfluoropropene were studied. Mainly the 1:1 adducts were obtained in excellent yields, but in the addition of di-ethyl ether and dioxane the 1:2 adduct with a symmetrical structure was produced along with the 1:1 adduct. The ethers containing the perfluoropropenyl group were prepared by the dehydrofluorination of the corresponding 1:1 adduct. From the proton and fluorine NMR spectra, the attacks of the α-ethereal and α-hydroxyalkyl radicals were found to occur exclusively on the difluoromethylene carbon. The relative reactivities of ethers and alcohols were determined by competitive reaction.

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